Ring Folding in of Cyclopentadienyl Diazabutadiene Complexes

of Group 4 and 5 Transition Metals.

Andrew J. Churchill, Jennifer C. Green,* Aidan G. Moody and Matthias Müller.

Department of Chemistry, Inorganic Chemistry Laboratory, South Parks Road,

Oxford OX1 3QR, UK.

Electronic Supplementary Information

1. Crystal structure data.

2. Cartesian coordinates for optimized structures.

3. Variable temperature 1H NMR spectra (in separate file ESI_2.docx)

Crystal Data

a = 14.2510(10) Å α = 90°b = 9.7150(10) Å β = 104.94(2)°c = 17.1330(10) Å γ = 90°Volume 2291.9(4) ų Crystal Class MonoclinicSpace group P 1 21/n 1 Z = 4Formula C21 H37 N4 Nb1 Mr 438.46Cell determined from 29624 reflections Cell θ range = 0 - 0°Temperature 293KPressure 1 kPa Shape prismColour colourless Size 0.26 × 0.66 × 1.28 mmDx 1.27 Mg m-3 F000 928.000μ 0.536 mm-1

Absorption correction multi-scan Tmin 0.70 Tmax 0.87 Data CollectionDiffractometer DIP Scan type ω scansReflections measured 29624Independent reflections 4552Rint 0.064θmax 90.0000h = -17 → 98k = 0 → 14l = 0 → 66RefinementΔρmin = -0.84 e Å-3

Δρmax = 0.74 e Å-3

Reflections used 4552Cutoff: I > -3.00σ(I)Parameters refined 235S = 0.96R-factor 0.059weighted R-factor 0.102Δ/σmax 0.0011Refinement on F²w = w′ × [1 - (ΔFobs / 6 × ΔFest)²]²

w′ = [P0T0′(x) + P1T1′(x) + ...Pn-1Tn-1′(x)]-1,where Pi are the coefficients of a Chebychev series in ti(x), and x = Fcalc²/Fcalc²max.

P0 - Pn-1 = 153. 247. 159. 68.7 15.9 ParametersLabel x y z Uiso/equiv OccupancyNb1 .023660(17) 0.05481(3) .733638(14) 0.0336 1.0000

N1 0.11270(19) 0.1120(3) 0.66099(17) 0.0468 1.0000 N2 -0.0286(2) -0.1179(3) 0.66204(16) 0.0465 1.0000

N3 -0.0132(2) 0.1603(3) 0.82777(16) 0.0446 1.0000 N4 0.07347(19) -0.0822(3) 0.82937(15) 0.0397 1.0000

C1 -0.1669(3) 0.2389(4) 0.6647(3) 0.0614 1.0000 C2 -0.1528(3) 0.0250(5) 0.5987(3) 0.0721 1.0000

C3 -0.1090(3) -0.0955(5) 0.5988(3) 0.0727 1.0000

C4 0.0142(3) -0.2556(4) 0.6659(2) 0.0595 1.0000 C5 -0.0144(3) 0.2997(4) 0.8601(2) 0.0623 1.0000

C6 -0.0408(3) 0.0554(4) 0.8684(3) 0.0571 1.0000 C7 0.0034(3) -0.0692(4) 0.8691(2) 0.0537 1.0000

C8 0.1555(2) -0.1742(4) 0.8630(2) 0.0486 1.0000 C11 -0.2621(3) 0.2065(6) 0.6863(4) 0.1025 1.0000

C12 -0.1840(4) 0.3257(6) 0.5871(3) 0.0983 1.0000 C41 -0.0530(5) -0.3639(5) 0.6864(4) 0.0984 1.0000

C42 0.0436(5) -0.2947(7) 0.5885(3) 0.1011 1.0000 C51 -0.1091(5) 0.3406(7) 0.8792(3) 0.1020 1.0000

C52 0.0712(4) 0.3155(5) 0.9350(3) 0.0861 1.0000 C81 0.1270(4) -0.3176(4) 0.8835(3) 0.0698 1.0000

C82 0.2229(3) -0.1064(5) 0.9374(3) 0.0713 1.0000 C90 0.0906(3) 0.2426(5) 0.6715(4) 0.0825 1.0000

C91 0.1024(3) 0.1255(6) 0.6338(3) 0.0758 1.0000 C92 0.1689(4) 0.0445(6) 0.6860(5) 0.0980 1.0000

C93 0.1981(4) 0.1153(11) 0.7560(4) 0.1254 1.0000 C94 0.1488(6) 0.2387(9) 0.7486(5) 0.1156 1.0000

H11 -0.1275(3) 0.2957(4) 0.7082(3) 0.0726 1.0000 H21 -0.2078(3) 0.0488(5) 0.5587(3) 0.0881 1.0000

H31 -0.1313(3) -0.1621(5) 0.5594(3) 0.0869 1.0000 H41 0.0734(3) -0.2542(4) 0.7101(2) 0.0698 1.0000

H51 -0.0036(3) 0.3634(4) 0.8190(2) 0.0739 1.0000 H61 -0.1076(3) 0.0580(4) 0.8728(3) 0.0694 1.0000

H71 -0.0340(3) -0.1516(4) 0.8729(2) 0.0645 1.0000 H81 0.1926(2) -0.1841(4) 0.8220(2) 0.0567 1.0000

H111 -0.2929(3) 0.2908(6) 0.6946(4) 0.1529 1.0000 H112 -0.2488(3) 0.1527(6) 0.7350(4) 0.1528 1.0000

H113 -0.3040(3) 0.1554(6) 0.6432(4) 0.1528 1.0000 H122 -0.2200(4) 0.4070(6) 0.5931(3) 0.1460 1.0000

H123 -0.1227(4) 0.3519(6) 0.5778(3) 0.1459 1.0000 H121 -0.2200(4) 0.2723(6) 0.5421(3) 0.1459 1.0000

H413 -0.0211(5) -0.4520(5) 0.6935(4) 0.1470 1.0000 H411 -0.0694(5) -0.3377(5) 0.7354(4) 0.1470 1.0000

H412 -0.1109(5) -0.3693(5) 0.6431(4) 0.1470 1.0000 H421 0.0772(5) -0.3812(7) 0.5957(3) 0.1558 1.0000

H422 0.0853(5) -0.2243(7) 0.5767(3) 0.1558 1.0000 H423 -0.0138(5) -0.3021(7) 0.5446(3) 0.1559 1.0000

H512 -0.1051(5) 0.4343(7) 0.8976(3) 0.1509 1.0000 H513 -0.1198(5) 0.2815(7) 0.9209(3) 0.1510 1.0000

H511 -0.1619(5) 0.3312(7) 0.8320(3) 0.1510 1.0000 H523 0.0732(4) 0.4074(5) 0.9556(3) 0.1269 1.0000

H521 0.0635(4) 0.2518(5) 0.9756(3) 0.1269 1.0000

H522 0.1307(4) 0.2957(5) 0.9204(3) 0.1269 1.0000 H811 0.1841(4) -0.3738(4) 0.9015(3) 0.1040 1.0000

H812 0.0936(4) -0.3128(4) 0.9258(3) 0.1038 1.0000 H813 0.0845(4) -0.3600(4) 0.8365(3) 0.1040 1.0000

H822 0.2784(3) -0.1630(5) 0.9580(3) 0.1081 1.0000 H823 0.1891(3) -0.0937(5) 0.9786(3) 0.1078 1.0000

H821 0.2443(3) -0.0183(5) 0.9232(3) 0.1079 1.0000 H901 0.0540(3) 0.3222(5) 0.6464(4) 0.1001 1.0000

H911 0.0759(3) 0.1073(6) 0.5766(3) 0.0913 1.0000 H921 0.1966(4) -0.0405(6) 0.6719(5) 0.1141 1.0000

H931 0.2490(4) 0.0857(11) 0.8025(4) 0.1491 1.0000 H941 0.1588(6) 0.3125(9) 0.7882(5) 0.1401 1.0000

Thermal ParametersLabel U11 U22 U33 U23 U13 U12

Nb1 0.02938(13) 0.03969(16) 0.03054(13) 0.00182(12) 0.00564(9) 0.00306(12) N1 0.0379(13) 0.0492(17) 0.0472(15) 0.0001(12) -0.0004(11) -0.0003(12)

N2 0.0474(15) 0.0467(17) 0.0400(14) -0.0038(12) 0.0013(12) 0.0015(12) N3 0.0476(14) 0.0453(17) 0.0407(13) -0.0024(12) 0.0107(11) 0.0050(12)

N4 0.0450(14) 0.0390(16) 0.0359(12) 0.0025(10) 0.0117(11) 0.0035(10) C1 0.0483(19) 0.051(2) 0.071(2) 0.0034(18) -0.0089(17) 0.0085(16)

C2 0.064(2) 0.072(3) 0.061(2) -0.013(2) -0.0187(19) 0.008(2) C3 0.073(3) 0.070(3) 0.058(2) -0.023(2) -0.015(2) 0.005(2)

C4 0.072(2) 0.051(2) 0.050(2) -0.0159(17) 0.0070(18) 0.0105(19) C5 0.097(3) 0.040(2) 0.0457(19) -0.0030(15) 0.0114(19) 0.0101(19)

C6 0.0536(19) 0.051(2) 0.075(2) 0.0038(19) 0.0320(18) 0.0041(18) C7 0.0491(18) 0.050(2) 0.066(2) 0.0027(18) 0.0227(17) -0.0066(16)

C8 0.0527(18) 0.050(2) 0.0429(16) 0.0067(15) 0.0132(14) 0.0140(16) C11 0.050(2) 0.100(5) 0.154(6) -0.002(4) 0.021(3) 0.018(3)

C12 0.112(4) 0.066(3) 0.086(3) 0.021(3) -0.032(3) 0.002(3) C41 0.121(5) 0.050(3) 0.115(4) -0.010(3) 0.015(4) -0.015(3)

C42 0.121(4) 0.114(5) 0.065(3) -0.028(3) 0.020(3) 0.040(4) C51 0.124(5) 0.098(4) 0.090(4) -0.008(3) 0.037(3) 0.055(4)

C52 0.127(4) 0.066(3) 0.054(2) -0.014(2) 0.003(3) -0.010(3) C81 0.095(3) 0.050(3) 0.067(2) 0.0122(19) 0.026(2) 0.017(2)

C82 0.065(2) 0.083(3) 0.053(2) 0.008(2) -0.0082(18) 0.010(2) C90 0.068(3) 0.050(3) 0.141(5) 0.032(3) 0.048(3) -0.004(2)

C91 0.076(3) 0.106(4) 0.052(2) 0.015(2) 0.027(2) -0.023(3) C92 0.065(3) 0.081(4) 0.175(6) 0.040(4) 0.079(4) 0.018(3)

C93 0.045(3) 0.223(9) 0.093(4) 0.085(5) -0.009(3) -0.055(4) C94 0.123(5) 0.137(6) 0.112(5) -0.062(5) 0.075(5) -0.100(5)

Cartesian coordinates for optimized structures.

TiCp2H-DAB C2v S=1

H -1.34871000 -1.25359000 2.70290210Ti 0.00000000 0.00000000 0.06486210H -2.18632000 -2.20115000 0.32332210H 1.34871000 -1.25359000 2.70290210H 0.00000000 -2.76039000 -1.16383790C 1.15267000 2.07402000 0.63328210C 0.00000000 2.38428000 -0.14494790C -1.15267000 2.07402000 0.63328210C -0.71177000 1.57594000 1.88425210C 0.71177000 1.57594000 1.88425210H 0.00000000 2.76039000 -1.16383790H -2.18632000 2.20115000 0.32332210H -1.34871000 1.25359000 2.70290210H 1.34871000 1.25359000 2.70290210H 2.18632000 -2.20115000 0.32332210C 1.15267000 -2.07402000 0.63328210C 0.71177000 -1.57594000 1.88425210C -0.71177000 -1.57594000 1.88425210C -1.15267000 -2.07402000 0.63328210C 0.00000000 -2.38428000 -0.14494790H 2.18632000 2.20115000 0.32332210N -1.29648000 0.00000000 -1.60823790N 1.29648000 0.00000000 -1.60823790C -0.70311000 0.00000000 -2.80975790C 0.70311000 0.00000000 -2.80975790H 2.31549000 0.00000000 -1.64766790H 1.27023000 0.00000000 -3.74551790H -1.27023000 0.00000000 -3.74551790H -2.31549000 0.00000000 -1.64766790

TiCp2H-DAB S=0

H 0.26044428 0.87976317 3.01064579Ti -0.00233696 0.07649422 0.04458823H 2.24801910 1.71904972 1.38672070H -2.09359101 1.48646547 1.83513114H 1.10771847 2.88861544 -0.76858175C -0.98739482 -2.11973161 0.60339333C 0.09533447 -2.39008753 -0.27727278C 1.29883056 -1.99869368 0.37024970C 0.96355719 -1.50540573 1.65352103C -0.45406306 -1.58042407 1.79806984H 0.01477093 -2.79787967 -1.27890215H 2.30030976 -2.07263445 -0.04403487H 1.66419346 -1.13328974 2.39583904

H -1.02597778 -1.27553902 2.67006529H -1.54669938 2.74651414 -0.49432285C -0.82062244 2.38447457 0.22581138C -1.10467716 1.70447726 1.43966206C 0.13517301 1.37734581 2.05541624C 1.18187172 1.82684242 1.20344209C 0.58608546 2.45976141 0.08042833H -2.03846405 -2.30218510 0.39841091N 1.12725677 0.25409384 -1.64388770N -1.46147571 0.11695654 -1.37958864C 0.44870737 -0.38075536 -2.64004722C -0.93503199 -0.45411724 -2.49872322H -2.46202684 0.30362798 -1.40280488H -1.55930436 -0.93126476 -3.26096081H 0.95292408 -0.79798053 -3.51758712H 2.07726705 0.54468579 -1.86648322

TiCp2i-PrDAB

H 2.93030716 1.16675725 -0.17340200Ti 0.11289373 -0.10935763 -0.05864815H 1.32557379 1.69482900 -2.27621415H 1.53265501 1.62985576 2.08656372H -1.04641945 2.55259188 -1.30198854C 1.03359478 -2.16764344 1.01558980C 0.28910994 -2.62031204 -0.10724377C 0.92501265 -2.13053748 -1.28023197C 2.06645113 -1.39359142 -0.88485181C 2.13370126 -1.41645548 0.53827433H -0.61015464 -3.22572047 -0.07446487H 0.60609754 -2.31133741 -2.30192001H 2.76643461 -0.89896871 -1.55256846H 2.89427656 -0.94244181 1.15255196H -0.91981782 2.51269540 1.36719588C -0.11373740 2.24151031 0.69450119C 1.16848753 1.76063781 1.07074481C 1.90280848 1.50819771 -0.11958917C 1.05944442 1.79490006 -1.22703589C -0.18069795 2.26257991 -0.71698198H 0.81200768 -2.38154908 2.05644320N -1.48204471 -0.22649336 -1.32529716N -1.35223583 -0.26697314 1.35203392C -2.33282817 -1.04947768 -0.65175415C -2.26536178 -1.07055330 0.73942689H -2.34997605 -1.81044728 3.50309542H -2.91647480 -1.74773946 1.30609553H -3.03669535 -1.71021475 -1.17295051H -3.97142770 0.37443225 -2.47471114C -1.80794308 0.17175614 -2.69995502

H -0.98029963 0.81886323 -3.02552333C -1.87114774 -1.01564545 -3.67637866H -0.92992152 -1.57962521 -3.66955221H -2.05399583 -0.65993422 -4.70119585H -2.68699350 -1.70554527 -3.41496563C -3.10776592 0.99263665 -2.76035058H -3.06739245 1.84511905 -2.06881691H -3.28134296 1.37404353 -3.77779916C -1.54351675 0.08957574 2.76300141H -0.68796493 0.72871250 3.02616932C -2.83100248 0.90520007 2.97306243H -2.85720666 1.77793944 2.30656513H -2.90526316 1.25583060 4.01342400H -3.71854556 0.29370448 2.75393030C -1.51264541 -1.12639825 3.70523235H -0.57652789 -1.68737328 3.59115495H -1.59595374 -0.80168571 4.75300900

ZrCp2H-DAB C2v S=0

H 0.24503330 0.99219063 3.05881736Zr -0.00596491 0.01095925 0.01332978H 2.24314735 1.82148729 1.44149235H -2.10151097 1.60534698 1.87027232H 1.11908943 2.95331222 -0.74236502C -0.98480457 -2.28625371 0.76951894C 0.10657890 -2.60611383 -0.08520706C 1.30591461 -2.17989069 0.55033785C 0.95675928 -1.61539142 1.80502711C -0.45788950 -1.68113009 1.94043500H 0.03646946 -3.09010169 -1.05311154H 2.31246212 -2.29324342 0.15749082H 1.65144411 -1.20936619 2.53545741H -1.03603213 -1.33400799 2.79261442H -1.54172003 2.82139567 -0.47960149C -0.81742566 2.46474382 0.24553194C -1.10999499 1.80070781 1.46941186C 0.12594627 1.47611107 2.09522065C 1.17819790 1.91445305 1.24358820C 0.58876081 2.53462597 0.10677734H -2.03278347 -2.49504704 0.57331972N 1.20305576 0.18409255 -1.75240215N -1.53091890 0.05381056 -1.49732950C 0.47829595 -0.61739804 -2.60694620C -0.90398766 -0.68321194 -2.47799667H -2.53719062 0.15596042 -1.60702964H -1.46616529 -1.36508391 -3.12583565H 0.97298645 -1.24904978 -3.35324582H 2.15781400 0.37907186 -2.04473860

ZrCp2H-DAB

H 1.34837290 1.29467817 2.74820404Zr 0.00000000 -0.00000069 -0.04832691H 2.17865692 2.36687099 0.40922914H -1.34837290 1.29467817 2.74820404H 0.00000000 3.01121902 -1.03546547C -1.14567662 -2.21394296 0.71283498C 0.00000000 -2.58470579 -0.03700276C 1.14567662 -2.21394296 0.71283498C 0.70745935 -1.65170152 1.94703611C -0.70745935 -1.65170152 1.94703611H 0.00000000 -3.01122040 -1.03546547H 2.17865692 -2.36687237 0.40922914H 1.34837290 -1.29467955 2.74820404H -1.34837290 -1.29467955 2.74820404H -2.17865692 2.36687099 0.40922914C -1.14567662 2.21394158 0.71283498C -0.70745935 1.65170014 1.94703611C 0.70745935 1.65170014 1.94703611C 1.14567662 2.21394158 0.71283498C 0.00000000 2.58470441 -0.03700276H -2.17865692 -2.36687237 0.40922914N 1.31218746 -0.00000069 -1.72447052N -1.31218746 -0.00000069 -1.72447052C 0.67990167 -0.00000069 -2.97650425C -0.67990167 -0.00000069 -2.97650425H -2.32928415 -0.00000069 -1.78660463H -1.27309360 -0.00000069 -3.89107134H 1.27309360 -0.00000069 -3.89107134H 2.32928415 -0.00000069 -1.78660463

ZrCp2i-PrDAB

H 1.35117638 -3.85810801 0.25450602Zr -0.00000149 -0.90688147 -0.18141110H 2.18366387 -2.00350525 2.02376899H -1.35117936 -3.85810801 0.25450602H -0.00000149 -0.85228200 3.11233854C -1.15094400 -1.66291391 -2.34866698C -0.70688965 -0.34024007 -2.62665583C 0.70688667 -0.34024007 -2.62665583C 1.15094102 -1.66291391 -2.34866698C -0.00000149 -2.48446242 -2.19498355H -1.33950408 0.52769751 -2.78140897H 1.33950110 0.52769751 -2.78140897H 2.18523335 -1.99414619 -2.29832351H -0.00000149 -3.55315856 -2.00854561H -2.18366685 -2.00350525 2.02376899

C -1.15104809 -2.23007900 1.77473521C -0.71080258 -3.21372999 0.85101941C 0.71079960 -3.21372999 0.85101941C 1.15104511 -2.23007900 1.77473521C -0.00000149 -1.62815104 2.35447891H -2.18523633 -1.99414619 -2.29832351N 1.39710610 0.67468934 0.16119878N -1.39710908 0.67468934 0.16119878C 0.69668333 1.30539701 1.16323675C -0.69668631 1.30539701 1.16323675H -2.55047474 3.21683761 0.10187753H -1.21182172 1.73503545 2.03267611H 1.21181874 1.73503545 2.03267611H 3.45615703 1.53682392 1.91614919C 2.78436441 1.05752897 -0.11576114H 3.12314205 0.37280528 -0.90806392C 2.87285926 2.49210743 -0.66036015H 2.22006601 2.61533281 -1.53525875H 3.90474801 2.73739147 -0.95354530H 2.55047176 3.21683761 0.10187753C 3.71955184 0.86154460 1.08875863H 3.66483772 -0.17146532 1.45715322H 4.76100322 1.07607941 0.80722115C -2.78436739 1.05752897 -0.11576114H -3.12314503 0.37280528 -0.90806392C -3.71955482 0.86154460 1.08875863H -3.66484070 -0.17146532 1.45715322H -4.76100620 1.07607941 0.80722115H -3.45616001 1.53682392 1.91614919C -2.87286224 2.49210743 -0.66036015H -2.22006899 2.61533281 -1.53525875H -3.90475099 2.73739147 -0.95354530

HfCp2H-DAB C2v S=0

H 1.34533542 1.21724366 2.70627611Hf 0.00190022 0.01300391 0.02010906H 2.18059951 2.32010028 0.38911376H -1.35213460 1.21430777 2.70223385H 0.00038393 2.98014976 -1.05248920C -1.15065795 -2.20472304 0.65079227C 0.00207045 -2.57092349 -0.09738815C 1.15124255 -2.20499532 0.65632326C 0.70860962 -1.63785617 1.88083003C -0.71374526 -1.63777357 1.87743162H 0.00435170 -3.03215656 -1.07879212H 2.18456544 -2.35964716 0.35918204H 1.34593305 -1.28110776 2.68484212H -1.35485556 -1.28106221 2.67842576

H -2.18290495 2.31528289 0.38255359C -1.15026251 2.17281074 0.68935007C -0.71204612 1.58899363 1.90942187C 0.70680039 1.59056749 1.91154929C 1.14737970 2.17546889 0.69288066C -0.00068433 2.54375199 -0.05935099H -2.18256081 -2.35935998 0.34875255N 1.35298726 0.09873262 -1.59731631N -1.33856667 0.09805625 -1.60586572C 0.70195429 -0.63084833 -2.57788538C -0.68103032 -0.63112818 -2.58233696H -2.31502772 0.30428117 -1.79961882H -1.23017617 -1.23484875 -3.31167028H 1.25620446 -1.23428539 -3.30356210H 2.33064185 0.30484375 -1.78513516

HfCp2H-DAB

H -1.34862326 -1.26244214 2.77802285Hf 0.00000000 -0.00000155 0.00124581H -2.17864977 -2.32742538 0.43704090H 1.34862326 -1.26244214 2.77802285H 0.00000000 -2.96573811 -1.01044372C 1.14602404 2.18098034 0.74368608C 0.00000000 2.54907369 -0.00771205C -1.14602404 2.18098034 0.74368608C -0.70812772 1.62025094 1.97715292C 0.70812772 1.62025094 1.97715292H 0.00000000 2.96573502 -1.01044372H -2.17864977 2.32742229 0.43704090H -1.34862326 1.26243905 2.77802285H 1.34862326 1.26243905 2.77802285H 2.17864977 -2.32742538 0.43704090C 1.14602404 -2.18098343 0.74368608C 0.70812772 -1.62025403 1.97715292C -0.70812772 -1.62025403 1.97715292C -1.14602404 -2.18098343 0.74368608C 0.00000000 -2.54907678 -0.00771205H 2.17864977 2.32742229 0.43704090N -1.31379871 -0.00000155 -1.62796070N 1.31379871 -0.00000155 -1.62796070C -0.67899327 -0.00000155 -2.88582225C 0.67899327 -0.00000155 -2.88582225H 2.32976404 -0.00000155 -1.68736564H 1.27464507 -0.00000155 -3.79797625H -1.27464507 -0.00000155 -3.79797625H -2.32976404 -0.00000155 -1.68736564

HfCp2i-PrDAB

H 1.35123361 -3.82095996 0.29628237Hf -0.00000064 -0.89173494 -0.15983492H 2.18277673 -1.92734336 2.02375591H -1.35123489 -3.82095996 0.29628237H -0.00000064 -0.75239568 3.08713129C -1.15058329 -1.67577645 -2.28432539C -0.70668069 -0.35741861 -2.58409799C 0.70667941 -0.35741861 -2.58409799C 1.15058201 -1.67577645 -2.28432539C -0.00000064 -2.49581600 -2.12272114H -1.33905207 0.50886171 -2.74841066H 1.33905079 0.50886171 -2.74841066H 2.18473338 -2.00618559 -2.22747721H -0.00000064 -3.56106681 -1.92014242H -2.18277801 -1.92734336 2.02375591C -1.15065927 -2.16119049 1.78139441C -0.71063592 -3.16687391 0.88174360C 0.71063464 -3.16687391 0.88174360C 1.15065799 -2.16119049 1.78139441C -0.00000064 -1.54720885 2.34944548H -2.18473466 -2.00618559 -2.22747721N 1.37956406 0.66515220 0.17003738N -1.37956534 0.66515220 0.17003738C 0.69417478 1.35550490 1.15122409C -0.69417606 1.35550490 1.15122409H -2.56729314 3.19444260 0.06598016H -1.22216976 1.82084939 1.99306739H 1.22216848 1.82084939 1.99306739H 3.46997965 1.50941886 1.88212160C 2.76562846 1.02988262 -0.13815249H 3.08309970 0.33417900 -0.92997772C 2.86526708 2.45881092 -0.69571458H 2.19854579 2.58591677 -1.55955009H 3.89527033 2.68712128 -1.00857410H 2.56729186 3.19444260 0.06598016C 3.72048558 0.83310090 1.05147298H 3.66981833 -0.19910388 1.42263032H 4.75840046 1.04514558 0.75480953C -2.76562974 1.02988262 -0.13815249H -3.08310098 0.33417900 -0.92997772C -3.72048686 0.83310090 1.05147298H -3.66981961 -0.19910388 1.42263032H -4.75840174 1.04514558 0.75480953H -3.46998093 1.50941886 1.88212160C -2.86526836 2.45881092 -0.69571458H -2.19854707 2.58591677 -1.55955009H -3.89527161 2.68712128 -1.00857410

NbCp2H-DAB S=1/2

H -1.34564336 1.28289390 -2.76839715Nb 0.00000000 -0.00000000 0.03191275H -2.18259988 2.24458556 -0.38592249H 1.34564336 1.28289390 -2.76839715H 0.00000000 2.83048892 1.09090950C 1.14906826 -2.09609972 -0.68797051C 0.00000000 -2.44006051 0.07823698C -1.14906826 -2.09609972 -0.68797051C -0.70440957 -1.61705178 -1.95780695C 0.70440957 -1.61705178 -1.95780695H 0.00000000 -2.83048892 1.09090950H -2.18259988 -2.24458556 -0.38592249H -1.34564336 -1.28289390 -2.76839715H 1.34564336 -1.28289390 -2.76839715H 2.18259988 2.24458556 -0.38592249C 1.14906826 2.09609972 -0.68797051C 0.70440957 1.61705178 -1.95780695C -0.70440957 1.61705178 -1.95780695C -1.14906826 2.09609972 -0.68797051C 0.00000000 2.44006051 0.07823698H 2.18259988 -2.24458556 -0.38592249N -1.23697391 -0.00000000 1.71705093N 1.23697391 -0.00000000 1.71705093C -0.68300299 -0.00000000 2.98300299C 0.68300299 -0.00000000 2.98300299H 2.25691235 -0.00000000 1.70808624H 1.30459734 -0.00000000 3.87799428H -1.30459734 -0.00000000 3.87799428H -2.25691235 -0.00000000 1.70808624

NbCp2i-PrDAB S=1/2

H 2.59842828 1.66006059 -1.44612459Nb 0.03867250 -0.06351602 -0.04750831H 0.08207167 2.25279594 -2.21401547H 2.66740970 1.64019300 1.24493166H -1.41718507 2.58817183 0.01072851C 1.14451628 -2.02945288 1.05050901C 0.39899143 -2.48196167 -0.07479135C 1.06276905 -2.01659545 -1.24469311C 2.25494063 -1.34466256 -0.83882505C 2.30542567 -1.35312414 0.56829466H -0.53337349 -3.03721749 -0.04498008H 0.75909915 -2.20965459 -2.26982865H 2.98000528 -0.88530642 -1.50464164H 3.07651674 -0.90129560 1.18574100H 0.19418422 2.22015083 2.14951909

C 0.48262786 2.12064533 1.10677398C 1.79869859 1.84714757 0.62639823C 1.76256389 1.85746948 -0.78100240C 0.42352362 2.13715013 -1.18908146C -0.35897346 2.34768024 -0.01849145H 0.91515221 -2.23542153 2.09235755N -1.65065500 -0.31029404 -1.26676553N -1.57334361 -0.33492408 1.26722373C -2.86765940 -0.50768462 -0.64624563C -2.82602756 -0.52107224 0.71828615H -2.93380327 -1.90466559 3.18655377H -3.70834547 -0.66715557 1.34180387H -3.78647406 -0.64182034 -1.21755040H -3.52924847 0.74831070 -3.09722902C -1.63526299 -0.28798798 -2.74052575H -0.58427083 -0.12319999 -3.02336345C -2.07564554 -1.62964684 -3.35055106H -1.48569905 -2.45949619 -2.93946495H -1.95115984 -1.61803756 -4.44380677H -3.13456831 -1.83266064 -3.13441729C -2.45923857 0.87635428 -3.31617230H -2.14144910 1.83348645 -2.88192213H -2.34302091 0.93078992 -4.40904196C -1.46798601 -0.34328777 2.73746799H -0.40234042 -0.17887511 2.95907189C -2.25981308 0.80425863 3.38724408H -1.97403013 1.77192966 2.95410336H -2.07590361 0.83685358 4.47165590H -3.34084040 0.67467838 3.23286533C -1.86492638 -1.69989617 3.34414929H -1.29628160 -2.51737253 2.88148022H -1.67601710 -1.71036408 4.42814416

TaCp2H-DAB S=1/2

H 1.34542002 1.24942585 2.76519644Ta 0.00000000 -0.00000000 -0.02375832H 2.18450056 2.21446819 0.38613461H -1.34542002 1.24942585 2.76519644H 0.00000000 2.80179078 -1.09294359C -1.15121762 -2.06539614 0.68660308C 0.00000000 -2.41208613 -0.07986753C 1.15121762 -2.06539614 0.68660308C 0.70500439 -1.58788074 1.95584461C -0.70500439 -1.58788074 1.95584461H 0.00000000 -2.80179078 -1.09294359H 2.18450056 -2.21446819 0.38613461H 1.34542002 -1.24942585 2.76519644H -1.34542002 -1.24942585 2.76519644

H -2.18450056 2.21446819 0.38613461C -1.15121762 2.06539614 0.68660308C -0.70500439 1.58788074 1.95584461C 0.70500439 1.58788074 1.95584461C 1.15121762 2.06539614 0.68660308C 0.00000000 2.41208613 -0.07986753H -2.18450056 -2.21446819 0.38613461N 1.22973627 -0.00000000 -1.68730645N -1.22973627 -0.00000000 -1.68730645C 0.68042035 -0.00000000 -2.96465339C -0.68042035 -0.00000000 -2.96465339H -2.24843832 -0.00000000 -1.67060393H -1.30840528 -0.00000000 -3.85405099H 1.30840528 -0.00000000 -3.85405099H 2.24843832 -0.00000000 -1.67060393

TaCp2i-PrDAB S=1/2

H 1.34582537 -1.24859025 -3.59058366Ta -0.00000085 0.00000000 -0.77370608H 2.18433195 -2.22489620 -1.22229581H -1.34582707 -1.24859025 -3.59058366H -0.00000085 -2.81800960 0.26162327C -1.15045278 2.06819661 -1.51473940C -0.00000085 2.41470696 -0.74646667C 1.15045108 2.06819661 -1.51473940C 0.70450185 1.58699586 -2.78190365C -0.70450355 1.58699586 -2.78190365H -0.00000085 2.81800960 0.26162327H 2.18433195 2.22489620 -1.22229581H 1.34582537 1.24859025 -3.59058366H -1.34582707 1.24859025 -3.59058366H -2.18433365 -2.22489620 -1.22229581C -1.15045278 -2.06819661 -1.51473940C -0.70450355 -1.58699586 -2.78190365C 0.70450185 -1.58699586 -2.78190365C 1.15045108 -2.06819661 -1.51473940C -0.00000085 -2.41470696 -0.74646667H -2.18433365 2.22489620 -1.22229581N 1.26113466 0.00000000 0.87739843N -1.26113636 0.00000000 0.87739843C 0.68003052 0.00000000 2.13870043C -0.68003222 0.00000000 2.13870043H -3.15763710 1.30841638 2.52075757H -1.28381812 0.00000000 3.04536966H 1.28381642 0.00000000 3.04536966H 3.15763540 -1.30841638 2.52075757C 2.73376294 0.00000000 0.81761527H 2.98777627 0.00000000 -0.25349873

C 3.34564772 1.26760728 1.43810602H 2.91116448 2.17143476 0.99065928H 4.43507496 1.28891039 1.28402129H 3.15763540 1.30841638 2.52075757C 3.34564772 -1.26760728 1.43810602H 2.91116448 -2.17143476 0.99065928H 4.43507496 -1.28891039 1.28402129C -2.73376464 0.00000000 0.81761527H -2.98777797 0.00000000 -0.25349873C -3.34564942 -1.26760728 1.43810602H -2.91116618 -2.17143476 0.99065928H -4.43507666 -1.28891039 1.28402129H -3.15763710 -1.30841638 2.52075757C -3.34564942 1.26760728 1.43810602H -2.91116618 2.17143476 0.99065928H -4.43507666 1.28891039 1.28402129

NbCp(H-DAB)2 S=0

H 2.26885947 -0.58256392 -1.84694482Nb 0.05220551 -0.13605976 -0.12392635H -2.26617547 -2.06220825 0.78688333N 1.27590936 -0.34680264 -1.83142782N -1.20505313 -0.19239919 -1.81849976C -1.21636636 -1.91675890 1.02601650C -0.11101398 -2.53011348 0.36439285C 1.08374323 -2.08019487 1.00159852C 0.70676728 -1.22353431 2.07975707C -0.69892463 -1.12333762 2.09477133H -0.16750626 -3.20085081 -0.48751313H 2.09710420 -2.37141744 0.73937729H 1.38743564 -0.69454101 2.74053455H -1.28351447 -0.50436597 2.76919977C 0.72789495 -0.13165301 -3.06443220C -0.64755627 -0.04602018 -3.05738390H -2.21950816 -0.30484427 -1.82333804H -1.25516385 0.06716295 -3.95555859H 1.33556834 -0.09366770 -3.96888106H -2.08652487 1.76711745 0.23580889C -0.47922530 2.30082921 1.35995423C 0.90382530 2.21173064 1.35475674H 2.42101835 1.47727576 0.21904912H 1.53029977 2.83232686 2.00028635H -1.01611352 2.99643248 2.00969896N -1.12340128 1.51092279 0.44699490N 1.43460962 1.34628552 0.43745637

NbCp(i-PrDAB)2 S=0

Nb 0.38084349 0.55918150 12.47371455N -1.51691610 1.15432532 11.70591477N -0.32613390 -1.15050511 11.41065344N -0.25251665 1.48966196 14.30628342N 0.92914673 -0.82803977 14.02107921C -2.43738794 2.24560257 12.07427101C -1.85628670 0.42119057 10.60068614C -1.22878606 -0.79367025 10.44569077C 0.06319297 -2.57183291 11.44411294C -0.30901499 2.91082943 14.72338762C -0.44396109 0.56878766 15.30196929C 0.17685495 -0.64991438 15.15183044C 2.06844568 -1.76778728 14.14822453C -3.73843750 1.68615272 12.67103543C -2.72643085 3.22499297 10.92393567C -1.08946893 -3.44679444 11.96139203C 0.60174088 -3.09252329 10.10050545C -1.61560817 3.29755297 15.44000522C 0.89415156 3.27901922 15.60948531C 1.66111799 -3.17461549 14.62338253C 3.15737486 -1.20637270 15.07939143C 1.28903631 2.46888575 11.15335521C 1.43345132 1.26714277 10.40034805C 2.40432817 0.44882022 11.05668294C 2.83749169 1.13956382 12.21723769C 2.14776926 2.38450269 12.27697506H -1.92640234 2.81105110 12.85676155H -2.61288817 0.76519876 9.89217341H -1.46702823 -1.45377327 9.60866329H 0.88159778 -2.63660014 12.16442270H -0.24516954 3.50076350 13.79724060H -1.01103633 0.80898135 16.20429968H 0.12160464 -1.41443409 15.93021067H 2.49696611 -1.86172129 13.13968405H -4.39340905 2.50029162 13.01902163H -3.51272197 1.02471285 13.51784782H -4.29060519 1.10072350 11.92081500H -3.29692230 4.08694098 11.30064524H -1.79330456 3.59694431 10.47828749H -3.32453048 2.76213552 10.12585749H -0.77090175 -4.49601033 12.06359410H -1.43257467 -3.08259284 12.93882295H -1.94408174 -3.41583993 11.26924589H 1.00571290 -4.10818240 10.22582178H 1.40471504 -2.44521344 9.72123025H -0.18371785 -3.14621716 9.33293814H -1.65299941 4.38736007 15.58363035H -1.67667186 2.83621222 16.43600095H -2.49999538 2.99112195 14.86873644

H 0.90842016 4.35994816 15.81637755H 0.83797927 2.74594535 16.56961056H 1.84022051 2.99848854 15.12996111H 2.52032584 -3.85705603 14.54727309H 1.34667348 -3.16391528 15.67678711H 0.83707838 -3.58412179 14.02727456H 4.04316887 -1.85952522 15.07810051H 2.78129639 -1.13897294 16.11049740H 3.46256482 -0.19882347 14.77136829H 0.63625545 3.30066055 10.90665746H 0.89248280 1.01474496 9.49327653H 2.76081589 -0.51788733 10.71404116H 3.57116207 0.78804026 12.93538405H 2.26569053 3.13760739 13.04946148

TaCp(H-DAB)2 S=0

H 2.40840862 -0.46518096 -1.63656403Ta 0.05654171 -0.11377067 -0.12361780H -2.24543730 -1.32531042 1.65731674N 1.40795425 -0.27898035 -1.70298659N -1.06688368 -0.29754452 -1.87045605C -1.19644569 -1.53515686 1.47090881C -0.68219444 -2.41679597 0.48435152C 0.74118916 -2.40595839 0.58003787C 1.10529003 -1.51754317 1.62557984C -0.09222472 -0.97109949 2.17859330H -1.26022416 -2.98481480 -0.23815105H 1.41927427 -2.96433192 -0.05808066H 2.11648159 -1.29225057 1.95101134H -0.15172974 -0.24473893 2.98284455C 0.93739826 -0.14604404 -2.99098201C -0.42913704 -0.15635604 -3.08349734H -2.06418352 -0.49919427 -1.93920864H -0.98277463 -0.10215758 -4.01993361H 1.61131865 -0.08253375 -3.84432547H -2.20258089 1.63342584 0.02320842C -0.75091853 2.24182500 1.32559358C 0.62633983 2.25224997 1.41844578H 2.24877703 1.66684463 0.32358122H 1.16477852 2.89521181 2.11841794H -1.38797585 2.87603630 1.94626868N -1.26807497 1.40965679 0.35811178N 1.28110197 1.42891900 0.52985698

TaCp(i-PrDAB)2

Ta 0.36272300 0.54979900 12.47455100N -1.50394700 1.15063800 11.70441400N -0.31873000 -1.14138900 11.41872000

N -0.24587500 1.48909800 14.27725700N 0.94440500 -0.81558700 13.99086500C -2.42236000 2.24432900 12.06907700C -1.85416500 0.41353100 10.59341500C -1.22878700 -0.79584500 10.44270900C 0.06419500 -2.56384400 11.46944300C -0.27672700 2.90360000 14.71826100C -0.46571500 0.55139900 15.26443900C 0.15950400 -0.65908500 15.11403900C 2.10990600 -1.71807300 14.14379400C -3.74653800 1.69698000 12.62341500C -2.66708900 3.24377200 10.92480900C -1.09374000 -3.43371000 11.98214100C 0.61354400 -3.09649600 10.13427200C -1.58623200 3.30518300 15.42250600C 0.91465400 3.23326900 15.63540400C 1.73879300 -3.13461600 14.62097600C 3.16282000 -1.12168500 15.09505200C 1.28818500 2.48713800 11.25353500C 1.37971100 1.32685400 10.42624800C 2.34508300 0.44871900 11.00626100C 2.83076500 1.05827800 12.19018600C 2.17880800 2.31552700 12.34269400H -1.92457200 2.79179200 12.87233400H -2.60542800 0.76665400 9.88508400H -1.45342100 -1.46120600 9.60744100H 0.87591600 -2.62486700 12.19752100H -0.18643300 3.50958900 13.80455800H -1.08325700 0.77420500 16.13677900H 0.06582400 -1.45039300 15.86039400H 2.55976100 -1.80673700 13.14379700H -4.40071800 2.51614000 12.96108800H -3.55303000 1.02429800 13.46942200H -4.28573400 1.12578100 11.85303600H -3.24099100 4.10656500 11.29462900H -1.71726700 3.61259900 10.51271100H -3.24331500 2.79754200 10.10147300H -0.78067300 -4.48445600 12.08663800H -1.43930700 -3.06664100 12.95760200H -1.94535200 -3.39949700 11.28639600H 1.01155500 -4.11328400 10.26948200H 1.42360400 -2.45649100 9.75715500H -0.16418700 -3.15115900 9.35890600H -1.60408300 4.39302600 15.58363100H -1.66900400 2.82921600 16.40998800H -2.46946800 3.02589600 14.83585900H 0.94107300 4.30889800 15.86739900H 0.83053300 2.67952100 16.58167100H 1.86736000 2.94881100 15.17182400

H 2.62082300 -3.78934200 14.56573600H 1.40523700 -3.12681100 15.66844900H 0.93963300 -3.57563000 14.01345400H 4.06778900 -1.74787200 15.11538100H 2.76206800 -1.06352000 16.11737500H 3.44403600 -0.10495600 14.79400000H 0.65276800 3.34871500 11.07438100H 0.80176500 1.13646000 9.52644800H 2.65489100 -0.51133100 10.60563300H 3.56818600 0.64181000 12.86775500H 2.33704300 3.01566000 13.15578100

Variable temperature NMR of CpNb(i-PrDAB)2 in C6D6.

Variable temperature NMR of CpTa(i-PrDAB)2 in C6D6.