esi fcpsnphg bh3 rev finals28 600 figure s37.maldi-tof mass spectrum of rac-5; the additional peaks...

S1

Supporting Information

Planar Chiral Ferrocenylphosphine-borane Complexes Featuring Agostic-type B‒H···E (E = Hg, Sn) Interactions

Alain C. Tagne Kuate,a,b Roger A. Lalancette,a* F. Jäklea*

aDepartment of Chemistry, Rutgers University-Newark, 73 Warren Street, Newark, NJ 07102,

USA

bDepartment of Chemistry, Faculty of Sciences, University of Dschang, P.O. Box 67, Dschang,

Cameroon

* To whom correspondence should be addressed.

Email: [email protected] ; [email protected]

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2017

S2

Reaction of rac-5 with PhBCl2: Isolation of FcPPh2·BH3 During the course of our studies we also attempted the synthesis of boron-bridged diferrocenes.

However, we could only isolate the parent species FcPPh2·BH3, presumable due to protonolysis.

The lack of analytical data on FcPPh2·BH3 in the literature encouraged us to perform a full

characterization. The MALDI-TOF mass spectrum of FcPPh2·BH3 showed a molecular ion peak

at m/z = 767.5008, suggesting the presence of a dimer with loss of H2.

Synthetic Procedure: A solution of rac-5 (0.052 g, 0.084 mmol) in toluene (10 mL) was slowly

added to a solution of PhBCl2 (0.007 g, 0.042 mmol, 0.5 equiv) in toluene (2 mL) at ‒27 oC

inside a glovebox. The mixture was stirred at room temperature for two days and heated at 90 oC

overnight in a sealed flask. A grey solid was formed, which was removed by filtration and the

solvent was evaporated in vacuum to leave a yellow-orange residue. The latter was taken in a

minimum of THF and passed through a plug of Al2O3 eluted with THF/hexane. The first band

was concentrated, dissolved in CH2Cl2, layered with hexanes and stored at ‒25 oC. An orange

solid crystallized that was identified to be ferrocenylphosphine-borane adduct FcPPh2·BH3.

Yield: 0.023 g (69%). 1H NMR (499.9 MHz, CDCl3, 25 oC): δ = 7.59 (m, 4H, Ph), 7.47 (m, 2H,

Ph), 7.41 (m, 4H, Ph), 4.51 (nr, 2H, Cp), 4.42 (nr, 2H, Cp), 4.10 (s, 5H, free Cp), 1.25 (brm, 3H,

BH3). 13C{1H} NMR (125.7 MHz, CDCl3, 25 oC): δ = 133.0 (d, 2JP,C = 9 Hz, o-Ph), 131.7 (d, 1JP,C = 59 Hz, i-Ph), 131.2 (s, p-Ph), 128.8 (d, 3JP,C = 10 Hz, m-Ph), 73.1 (d, JP,C = 10 Hz, Cp),

72.2 (d, 1JP,C = 8 Hz, Cp), 70.1 (s, free Cp), 69.1 (d, 1JP,C = 69 Hz, i-Cp-P). 31P{1H} NMR

(202.5 MHz, CDCl3, 25 oC): δ = 16.0 (nr). 11B{1H} NMR (160.4 MHz, CDCl3, 25 oC): ‒38.4

(nr). High-resolution MALDI-TOF MS (positive mode, anthracene): m/z 370.0545

([(FcPPh2)+H]+, 100%, calcd for 12C221H1911B56Fe31P 370.0568).

S3

Figure S1. 1H NMR spectrum of (pS)-3.

Figure S2. Expansions of the 1H NMR spectrum of (pS)-3.

S4

Figure S3a. 13C NMR spectrum of (pS)-3.

Figure S3b. Expansions of the 13C NMR spectrum of (pS)-3.

S5

Figure S4. 11B NMR spectrum of (pS)-3.

Figure S5. 31P NMR spectrum of (pS)-3.

Figure S6. 119Sn NMR spectrum of (pS)-3.

S6

Figure S7a. 1H NMR spectrum of (pS)-4.

S7

Figure S7b. Expansions of the 1H NMR spectrum of (pS)-4.


S8


S9




S10

Figure S12a. 1H NMR spectrum of rac-5.

Figure S12b. Expansions of the 1H NMR spectrum of rac-5.

S11

Figure S13a. 13C NMR spectrum of rac-5.

Figure S13b. Expansions of the 13C NMR spectrum of rac-5.

S12

Figure S14. 11B NMR spectrum of rac-5.

Figure S15. 31P NMR spectrum of rac-5.

S13

Figure S16a. 1H NMR spectrum of (pSpS)-6.

Figure S16b. Expansions of the 1H NMR spectrum of (pSpS)-6.

S14

Figure S17a. 13C NMR spectrum of (pSpS)-6.

Figure S17b. Expansions of the 13C NMR spectrum of (pSpS)-6.

S15

Figure S18. 11B NMR spectrum of (pSpS)-6.

Figure S19. 31P NMR spectrum of (pSpS)-6.

Figure S20a. 1H NMR spectrum of (pSpS)-7.

S16

Figure S20b. Expansions of the 1H NMR spectrum of (pSpS)-7.

S17

Figure S21a. 1H NMR spectrum of (pS)-8.

Figure S21b. Expansions of the 1H NMR spectrum of (pS)-8.

S18



S19




S20

Figure S26a. 1H NMR spectrum of (pRpR)-10.

Figure S26b. Expansions of the 1H NMR spectrum of (pRpR)-10.

S21

Figure S27a. 13C NMR spectrum of (pRpR)-10.

Figure S27b. Expansions of the 13C NMR spectrum of (pRpR)-10.

S22

Figure S28. 11B NMR spectrum of (pRpR)-10.

Figure S29. 31P NMR spectrum of (pRpR)-10.

Figure S30. 119Sn NMR spectrum of (pRpR)-10.

at119_119Sn_101816

60 40 20 0 -20 -40 -60 -80Chemical Shift (ppm)

-13.

088

S23

Figure S31a. 1H NMR spectrum of FcPPh2·BH3.

Figure S31b. Expansions of the 1H NMR spectrum of FcPPh2·BH3.

S24

Figure S32a. 13C NMR spectrum of FcPPh2·BH3.

Figure S32b. Expansions of the 13C NMR spectrum of FcPPh2·BH3.

S25

Figure S33. 11B NMR spectrum of FcPPh2·BH3.

Figure S34. 31P NMR spectrum of FcPPh2·BH3.

S26

Figure S35. MALDI-TOF mass spectrum of (pS)-3.

534.

0228

532.

0165

533.

0197

530.

0114

535.

0241

531.

0130

538.

0336

536.

0285

537.

0322

539.

0282

525.

3925

528.

0095

526.

0083

529.

0152

527.

0086

540.

2598

121416_AT34_calib_1_2 0:A1 MS Raw

0

1

2

3

4

4x10

Inte

ns. [

a.u.

]

534.

0222

532.

0220

533.

0237

530.

0217

531.

0235

535.

0250

536.

0243

538.

0249

539.

0279

528.

0245

537.

0268

529.

0261

526.

0244

527.

0275

540.

0305

0

500

1000

1500

2000

Inte

ns. [

a.u.

]

524 526 528 530 532 534 536 538 540 542

[M–BH3]+

S27


568.

0015

565.

9962

569.

0093

564.

9971

566.

9906

564.

0098

570.

0010

121416_AT44_calib_1_1 0:A3 MS Raw

0

50

100

150

200

Inte

ns. [

a.u.

]

568.

0001

566.

0003

567.

0020

565.

0023

564.

0008

569.

0019

569.

9995

0

500

1000

1500

2000

Inte

ns. [

a.u.

]

564 565 566 567 568 569 570

553.

9666

551.

9519

549.

9408

555.

9871

554.

9809

552.

9764

550.

9521

557.

9964

556.

9941

547.

9397

559.

0110

560.

0040

548.

9441

560.

9992

547.

1063

121416_AT44_calib_1_2 0:A3 MS Raw

0.0

0.2

0.4

0.6

0.8

1.0

5x10

Inte

ns. [

a.u.

]

553.

9669

551.

9668

552.

9685

555.

9664

549.

9671

554.

9689

550.

9688

557.

9693

556.

9690

558.

9723

559.

9683

547.

9694

548.

9714

560.

9707

546.

9729

0

500

1000

1500

2000

Inte

ns. [

a.u.

]

548 550 552 554 556 558 560

[M–BH3]+

[M]+

S28

Figure S37. MALDI-TOF mass spectrum of rac-5; the additional peaks at higher molecular weight correspond to [rac-6–BH3]+ (940.0842 Da) and an undetermined dimeric species.

605.

9874

603.

9795

602.

9759 60

4.98

80

606.

9909

607.

9944

601.

9743

609.

0013

609.

9928

600.

9813

599.

9767

121416_AT79_calib_1_1 0:A10 MS Raw

0.0

0.5

1.0

1.5

2.0

2.54x10

Inte

ns. [

a.u.

]

605.

9880

603.

9867

604.

9876

602.

9868

607.

9884

606.

9893

601.

9856

608.

9912

609.

9896

600.

9909

599.

9882

0

500

1000

1500

2000

Inte

ns. [

a.u.

]

600 602 604 606 608 610

[M–BH3]+

S29

Figure S38. MALDI-TOF mass spectrum of (pSpS)-6.

954.

1053

952.

0917

953.

0947

951.

0822

955.

1023

956.

0928

950.

0733

957.

0979

949.

0719

958.

0825

948.

0920

959.

0957

947.

0987

121416_AT100R_calib_1_2 0:A14 MS Raw

0

1

2

3

44x10

Inte

ns. [

a.u.

]

954.

1037

952.

1024

953.

1040

951.

1022

955.

1062

950.

1017

956.

1068

949.

1044

957.

1088

948.

1047

958.

1113

947.

1070

959.

1136

0

500

1000

1500

2000

Inte

ns. [

a.u.

]

948 950 952 954 956 958

940.

0734

938.

0680

941.

0755

937.

0652 9

39.0

696

936.

0558

942.

0749

935.

0703

943.

0773

934.

0598

121516_AT100_cal_1_1 0:A14 MS Raw

0.0

0.2

0.4

0.6

0.8

1.0

4x10

Inte

ns. [

a.u.

]

940.

0703

938.

0688

939.

0703

937.

0682

941.

0729

936.

0676

942.

0735

943.

0757

935.

0720

934.

0701

944.

0782

933.

0762

0

500

1000

1500

2000

Inte

ns. [

a.u.

]

934 936 938 940 942 944

[M–BH3]+

[M–2BH3]+

S30

Figure S39. MALDI-TOF mass spectrum of (pSpS)-7.

905.

0495

903.

0455

904.

0451

901.

0408

906.

0608

902.

0405

907.

0630

909.

0636

908.

0675

910.

0715

899.

0395

900.

0473

897.

0530

911.

0714

898.

0399

121416_AT64_III_calib_1_4 0:A6 MS Raw

0.00

0.25

0.50

0.75

1.00

1.25

4x10

Inte

ns. [

a.u.

]

905.

0517

903.

0517

904.

0533

906.

0542

901.

0513

902.

0531

907.

0547

909.

0543

908.

0566

910.

0569

899.

0543

900.

0561

897.

0538

911.

0596

898.

0569

912.

0621

0

500

1000

1500

2000

Inte

ns. [

a.u.

]

896 898 900 902 904 906 908 910 912

889.

0534

887.

0515

888.

0574

886.

0562

885.

0482

890.

0511

891.

0548

893.

0575

884.

0653

892.

0608

894.

0755

883.

0471

895.

0634

881.

0489

882.

0681

121416_AT64_III_calib_1_4 0:A6 MS Raw

0

1000

2000

3000

4000

5000

Inte

ns. [

a.u.

]

889.

0568

887.

0568

888.

0584

890.

0593

885.

0564

886.

0582

891.

0598

893.

0594

892.

0617

894.

0620

883.

0594

884.

0612

881.

0588

895.

0647

882.

0620

896.

0672

0

500

1000

1500

2000

Inte

ns. [

a.u.

]

882 884 886 888 890 892 894 896

[M–BH3 + O]+

[M–BH3 + H]+

S31


533.

0127

534.

9943

531.

0222

532.

0288

534.

0103

530.

0369

529.

0350

536.

0022

537.

0112

538.

9982

528.

0415

538.

0351

527.

0244

540.

0074

121616_AT64_II_cal_1_7 0:I1 MS Raw

0.0

0.5

1.0

1.5

4x10

Inte

ns. [

a.u.

]

534.

9936

532.

9934

533.

9952

530.

9932

531.

9949

535.

9965

536.

9957

538.

9963

539.

9993

528.

9959

537.

9982

529.

9975

526.

9958

527.

9989

0

500

1000

1500

2000

Inte

ns. [

a.u.

]

528 530 532 534 536 538 540

520.

0041

517.

9956

518.

9965

515.

9864

516.

9874

521.

0101

522.

0134

524.

0159

514.

9657

523.

0095

525.

0134

513.

9873

511.

9904

512.

9731

526.

0508

121616_AT64_II_cal_1_7 0:I1 MS Raw

0

1

2

3

4x10

Inte

ns. [

a.u.

]

520.

0065

518.

0063

519.

0081

516.

0061

517.

0078

521.

0094

522.

0086

524.

0092

525.

0122

514.

0089

523.

0111

515.

0104

512.

0087

513.

0119

526.

0148

0

500

1000

1500

2000

Inte

ns. [

a.u.

]

512 514 516 518 520 522 524 526

[M–BH3–H + O]+

[M–BH3]+

S32

Figure S41. MALDI-TOF mass spectrum of (pRpR)-10.

903.

0502

905.

0513

904.

0532

906.

0494

901.

0560

902.

0456

907.

0415

900.

0674

909.

0508

908.

0615

899.

0725

910.

0621

121516_AT119_cal_1_2 0:A16 MS Raw

0

100

200

300

400

500

600

Inte

ns. [

a.u.

]

905.

0517

903.

0517

904.

0533

906.

0542

901.

0513

902.

0531

907.

0547

909.

0543

908.

0566

910.

0569

899.

0543

900.

0561

897.

0538

911.

0596

898.

0569

0

500

1000

1500

2000

Inte

ns. [

a.u.

]

898 900 902 904 906 908 910

889.

0544

887.

0382

888.

0715

890.

0703

885.

0188

891.

0876

886.

0578

893.

0750

892.

0986

894.

0884

883.

0214

884.

0613

892.

6449

881.

0188

882.

0209

895.

1011

879.

0203

880.

0514

121416_AT119_calib_1_2 0:B16 MS Raw

0.00

0.25

0.50

0.75

1.00

1.25

5x10

Inte

ns. [

a.u.

]

889.

0568

887.

0568

888.

0584

890.

0593

885.

0564

886.

0582

891.

0598

893.

0594

892.

0617

894.

0620

883.

0594

884.

0612

881.

0588

895.

0647

882.

0620

896.

0672

879.

0629

880.

0661

0

500

1000

1500

2000

Inte

ns. [

a.u.

]

880 882 884 886 888 890 892 894 896

[M–2BH3 + O]+

[M–2BH3 + H]+

S33

Figure S42. MALDI-TOF mass spectrum of FcPPh2·BH3.

370.

0545

371.

0744

368.

0526

372.

0682

369.

0488

373.

0627

121916_FcPPh2BH3_II_cal_1_3 0:E11 MS Raw

0

1

2

3

4

5

4x10

Inte

ns. [

a.u.

]

370.

0568

371.

0600

368.

0615

372.

0624

369.

0649

373.

0646

0

500

1000

1500

2000

Inte

ns. [

a.u.

]

364 366 368 370 372 374 376 378

[M–2BH3 + O]+

[M–BH3 + H]+

S3

4

Tab

le S

1. C

ryst

al d

ata

and

stru

ctur

e re

finem

ent d

etai

ls fo

r (pS

)-3,

(pS)

-4, r

ac-5

, and

(pSp

S)-7

.

Com

poun

d (p

S)-3

(p

S)-4

ra

c-5

(pSp

S)-7

em

piric

al fo

rmul

a C

25H

30B

FePS

n C

24H

27B

ClF

ePSn

C

22H

21B

ClF

eHg

P C

46H

45B

Fe2P

2Sn

MW

54

6.81

56

7.22

61

9.06

90

0.96

T,

K

100

100

100

100

wav

elen

gth,

Å

1.54

178

1.54

178

1.54

178

1.54

178

crys

tal s

yste

m

Orth

orho

mbi

c O

rthor

hom

bic

Orth

orho

mbi

c O

rthor

hom

bic

spac

e gr

oup

P212

121

P212

121

Pbca

P2

1212

1 a,

Å

7.45

43(2

) 7.

3385

(2)

15.7

369(

8)

10.8

780(

2)

b, Å

16

.414

1(4)

16

.586

7(4)

15

.009

5(7)

17

.554

3(4)

c,

Å

19.3

128(

4)

19.1

137(

5)

17.5

758(

8)

20.7

334(

5)

α, d

eg

90

90

90

90

β, d

eg

90

90

90

90

γ, de

g 90

90

90

90

V,

Å3

2363

.0(1

) 23

26.5

(1)

4151

.5(3

) 39

59.1

6(15

) Z

4 4

8 4

ρ cal

c, g

cm-3

1.

537

1.61

9 1.

981

1.51

2 µ

(Cu

Kα

), m

m-1

14

.01

15.2

9 20

.61

11.7

8 cr

ysta

l siz

e, m

m

0.38×0

.21×

0.18

0.

26×0

.21×

0.07

0.

26×0

.18×

0.11

0.

29×0

.23×

0.17

θ

rang

e, d

eg

3.5–

70.5

3.

5–69

.5

4.8–

68.7

3.

3–68

.8

limiti

ng in

dice

s –8

≤ h

≤ 8

–2

0 ≤

k ≤

19

–23 ≤

l ≤ 2

2

–6 ≤

h ≤

8

–20 ≤

k ≤

18

–21 ≤

l ≤ 2

3

–16 ≤

h ≤

17

–17 ≤

k ≤

18

–20 ≤

l ≤ 2

0

–12 ≤

h ≤

12

–20 ≤

k ≤

21

–24 ≤

l ≤ 2

4 re

flns c

olle

cted

21

972

1595

5 36

723

3474

5 in

depe

nden

t ref

lns

4183

[R

(int)

= 0.

036]

38

13

[R(in

t) =

0.02

6]

3696

[R

(int)

= 0.

040]

68

72

[R(in

t) =

0.05

0]

abso

rptio

n co

rrec

tion

Num

eric

al

Num

eric

al

Num

eric

al

Num

eric

al

data

/rest

rain

ts/p

aram

eter

s 41

83/3

/274

38

13/0

/273

36

96/0

/256

68

72/3

/480

go

odne

ss-o

f-fit

on

F2

1.05

1.

03

1.13

0.

98

final

R in

dice

s, [ I

>2σ

(I) ]

[a]

0.01

6, w

R2 =

0.0

40

0.01

8, w

R2 =

0.0

38

0.02

2, w

R2 =

0.0

67

0.02

1, w

R2 =

0.0

44

R in

dice

s (al

l dat

a) [a

] 0.

017

0.01

9 0.

0256

0.

022

peak

max

/hol

e min

(e Å

–3)

0.38

/ –0

.35

0.50

/ –0

.41

0.83

/ –1

.15

0.27

/ –0

.31

abso

lute

stru

ctur

e pa

ram

eter

0.

038(

3)

0.02

0(3)

-

0.02

7(2)

[a] R1 = Σ||F o|–|F

c||/Σ|F

o|; w

R2 = {Σ[w

(Fo2

–Fc2) 2]/Σ[w(F

o2) 2]}1/2

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Computational Details for the Optimized Structures of (pS)-3 and (pS)-4

Compound (pS)-3

Stoichiometry C25H30BFePSn Framework group C1[X(C25H30BFePSn)] Deg. of freedom 171 Full point group C1 NOp 1 Largest Abelian subgroup C1 NOp 1 Largest concise Abelian subgroup C1 NOp 1 Selected Distances: H1···Sn1 = 3.129 Å, P1–B1 = 1.939 Å Standard orientation: Center Number Atomic Number Coordinates (Angstroms)

X Y Z

1 50 -2.58529 1.199284 0.337887 2 26 -0.790654 -1.935737 -0.611357 3 15 1.399948 0.439541 0.551407 4 5 0.739987 0.709201 2.337561 5 1 -0.091022 1.54001 2.151053 6 1 1.660059 1.215123 2.897112 7 1 0.398522 -0.358819 2.747869 8 6 -1.170403 0.07523 -0.810315 9 6 0.263758 -0.185455 -0.683922 10 6 0.655404 -1.062638 -1.769566 11 1 1.57566 -1.42283 -1.932356 12 6 -0.498517 -1.331822 -2.559508 13 1 -0.535087 -1.916885 -3.369736 14 6 -1.592088 -0.638033 -1.97695 15 1 -2.531896 -0.673382 -2.312814 16 6 -1.957743 -2.622607 0.930012 17 1 -2.604682 -2.076636 1.462663 18 6 -0.589706 -2.819927 1.234482 19 1 -0.103202 -2.435735 2.018957 20 6 -0.024525 -3.648508 0.22594 21 1 0.926355 -3.956572 0.177106 22 6 -1.050772 -3.954385 -0.702215 23 1 -0.952316 -4.521314 -1.520511 24 6 -2.250903 -3.322901 -0.267319 25 1 -3.140851 -3.367902 -0.721499 26 6 2.837419 -0.679918 0.453404 27 6 3.763507 -0.580296 -0.588939 28 1 3.664508 0.095568 -1.249582 29 6 4.826001 -1.463959 -0.657907 30 1 5.443169 -1.407464 -1.377637 31 6 4.993319 -2.437421 0.32516

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32 1 5.731654 -3.034477 0.284395 33 6 4.086155 -2.527813 1.356291 34 1 4.202716 -3.189376 2.027935 35 6 2.997506 -1.661788 1.423586 36 1 2.36777 -1.740552 2.131064 37 6 2.024339 2.03581 -0.066649 38 6 1.291715 2.826815 -0.936768 39 1 0.47601 2.496789 -1.296752 40 6 1.732783 4.09086 -1.290692 41 1 1.216565 4.627576 -1.880302 42 6 2.930994 4.576753 -0.779261 43 1 3.238723 5.442151 -1.022571 44 6 3.674737 3.791711 0.08608 45 1 4.498531 4.119828 0.428179 46 6 3.231018 2.530027 0.458346 47 1 3.739736 2.004961 1.06451 48 6 -4.412613 0.876052 -0.758687 49 1 -5.167185 1.243732 -0.252387 50 1 -4.545997 -0.085714 -0.892856 51 1 -4.35292 1.322257 -1.629088 52 6 -2.91545 0.560593 2.368493 53 1 -2.167507 -0.002804 2.658403 54 1 -3.750285 0.046688 2.417337 55 1 -2.978767 1.344524 2.951408 56 6 -2.046557 3.267888 0.334065 57 1 -1.163399 3.375373 0.743673 58 1 -2.707308 3.778643 0.844827 59 1 -2.02146 3.597443 -0.589347

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Compound (pS)-4

Stoichiometry C24H27BClFePSn Framework group C1[X(C24H27BClFePSn)] Deg. of freedom 162 Full point group C1 NOp 1 Largest Abelian subgroup C1 NOp 1 Largest concise Abelian subgroup C1 NOp 1 Selected Distances: H1···Sn1 = 2.631 Å, P1–B1 = 1.944 Å Standard orientation:

Center Number Atomic Number Coordinates (Angstroms)

X Y Z

1 50 -2.387491 1.053314 0.483656 2 26 -0.581954 -1.988349 -0.608665 3 17 -4.413978 0.647573 -0.741682 4 15 1.506943 0.497409 0.486467 5 5 0.731641 0.783261 2.225411 6 1 -0.135303 1.493664 1.988938 7 1 1.559874 1.289407 2.768124 8 1 0.454398 -0.182868 2.686438 9 6 -1.051563 -0.007618 -0.796202 10 6 0.380792 -0.192745 -0.724452 11 6 0.768098 -1.053679 -1.82369 12 1 1.695888 -1.370848 -2.021881 13 6 -0.392187 -1.37801 -2.560602 14 1 -0.429195 -1.969557 -3.365233 15 6 -1.503912 -0.740575 -1.944024 16 1 -2.454978 -0.815386 -2.246204 17 6 -1.745885 -2.757035 0.892977 18 1 -2.458775 -2.260495 1.38665 19 6 -0.389626 -2.826751 1.265923 20 1 0.025492 -2.395025 2.064962 21 6 0.28166 -3.607091 0.297166 22 1 1.257278 -3.826917 0.296554 23 6 -0.666676 -4.02463 -0.677975 24 1 -0.479761 -4.597013 -1.476591 25 6 -1.93308 -3.48983 -0.299277 26 1 -2.797622 -3.615034 -0.78561 27 6 2.066287 2.1125 -0.133623 28 6 1.232687 2.92263 -0.892193

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29 1 0.400481 2.584349 -1.2042 30 6 1.606482 4.225473 -1.202454 31 1 1.030393 4.77083 -1.725891 32 6 2.807298 4.730431 -0.750716 33 1 3.054246 5.625762 -0.951504 34 6 3.658284 3.921068 0.000565 35 1 4.496516 4.256278 0.293698 36 6 3.278619 2.629793 0.31862 37 1 3.850403 2.091511 0.852564 38 6 2.971578 -0.569082 0.426114 39 6 3.191457 -1.48142 1.436744 40 1 2.579852 -1.541903 2.161109 41 6 4.305864 -2.314384 1.399448 42 1 4.456598 -2.932401 2.1063 43 6 5.191114 -2.253965 0.346876 44 1 5.94783 -2.826981 0.322829 45 6 4.968048 -1.346089 -0.678138 46 1 5.564936 -1.310459 -1.41635 47 6 3.880512 -0.494362 -0.632667 48 1 3.748843 0.143066 -1.323557 49 6 -2.868549 0.319819 2.440408 50 1 -2.84552 1.060101 3.081112 51 1 -2.213835 -0.36047 2.703667 52 1 -3.76467 -0.077096 2.428536 53 6 -2.175888 3.165855 0.33518 54 1 -1.269819 3.423756 0.605279 55 1 -2.828189 3.601773 0.924183 56 1 -2.333224 3.445351 -0.590963

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Second Order Perturbation Theory Analysis of Fock Matrix in NBO Basis Compound (pS)-3:

E(2) E(j)-E(i) F(i,j) Donor NBO (i) Acceptor NBO (j) kcal/mol a.u. a.u. 8. BD (1) B4 - H5 / 133. LP*(1)Sn1 0.20 0.40 0.009

Compound (pS)-4: E(2) E(j)-E(i) F(i,j)

Donor NBO (i) Acceptor NBO (j) kcal/mol a.u. a.u. 7. BD (1) B5 - H6 / 134. LP*(2)Sn1 5.46 0.37 0.043

Atoms in Molecules (AIM) Analysis of Compound (pS)-4: Electron Density and Laplacian of the Electron Density at the BCPs: BCP # Name Atoms Rho DelSqRho Ellipticity K BPL - GBL_I 1 1 BCP1 Sn1-C9 0.058257 +0.441543 0.098363 +0.003085 0.000321 2 2 BCP2 Sn1-Cl3 0.031057 +0.263762 0.180649 +0.000203 0.001279 3 3 BCP3 Sn1-H6 0.008196 +0.040694 3.173225 -0.001239 0.027879 4 4 BCP4 P4-B5 0.117967 -0.123341 0.015182 +0.091664 0.000114 5 5 BCP5 B5-H6 0.163606 -0.186163 0.031616 +0.152568 0.000261 6 6 BCP6 B5-H7 0.167393 -0.261977 0.015456 +0.157056 0.000111 7 7 BCP7 B5-H8 0.165492 -0.233826 0.024250 +0.155217 0.000133 8 8 BCP8 Cl3-H16 0.006648 +0.026096 0.304853 -0.001318 0.109756 9 9 BCP9 Fe2-C10 0.053785 +0.263912 1.829033 +0.015711 0.379691 10 10 BCP10 P4-C10 0.167724 -0.281002 0.033883 +0.165734 0.001202 11 11 BCP11 C9-C10 0.282342 -0.794933 0.036028 +0.273013 0.020816 12 12 BCP12 C10-C11 0.291520 -0.729070 0.485689 +0.290491 0.009605 13 13 BCP13 C11-H12 0.279412 -0.986564 0.019557 +0.279439 0.001116 14 14 BCP14 C11-C13 0.295221 -0.823018 0.149306 +0.305908 0.089367 15 15 BCP15 Fe2-C13 0.049639 +0.369907 0.128523 +0.010907 0.170992 16 16 BCP16 C13-C15 0.294591 -0.824166 0.162673 +0.304573 0.087089 17 17 BCP17 C13-H14 0.277657 -0.885774 0.142848 +0.275465 0.010568 18 18 BCP18 Fe2-C9 0.053177 +0.250908 1.486597 +0.017293 0.272246 19 19 BCP19 C9-C15 0.296944 -0.735719 0.420427 +0.301185 0.023736 20 20 BCP20 C15-H16 0.280408 -0.981077 0.025007 +0.278860 0.000970 21 21 BCP21 Fe2-C19 0.049804 +0.265852 1.730782 +0.013919 0.951930 22 22 BCP22 Fe2-C21 0.049772 +0.274336 1.635907 +0.013260 1.013026 23 23 BCP23 C17-H18 0.279963 -0.983094 0.024664 +0.280751 0.001585 24 24 BCP24 H20-H40 0.003597 +0.012389 0.850014 -0.000924 0.383545 25 25 BCP25 H8-H20 0.005453 +0.018013 0.104974 -0.001096 0.077273 26 26 BCP26 Fe2-C25 0.051402 +0.381232 0.074650 +0.011728 0.146277 27 27 BCP27 C17-C19 0.301656 -0.801494 0.508203 +0.308525 0.011939 28 28 BCP28 C19-H20 0.280003 -0.985321 0.024571 +0.280537 0.001692 29 29 BCP29 C21-C23 0.300241 -0.794696 0.507503 +0.305909 0.012389 30 30 BCP30 C19-C21 0.293798 -0.952076 0.057943 +0.298352 0.002183 31 31 BCP31 C21-H22 0.278303 -0.975457 0.025058 +0.277941 0.001693 32 32 BCP32 C23-C25 0.293044 -0.799945 0.165894 +0.300031 0.089186 33 33 BCP33 C17-C25 0.293775 -0.806941 0.164471 +0.301336 0.088000 34 34 BCP34 C23-H24 0.277909 -0.972062 0.023815 +0.277608 0.001547 35 35 BCP35 C25-H26 0.277897 -0.888962 0.141866 +0.275800 0.009718 36 36 BCP36 P4-C27 0.163534 -0.301138 0.040719 +0.159916 0.000486 37 37 BCP37 C27-H54 0.002591 +0.006043 0.356704 -0.000427 0.248583 38 38 BCP38 C27-C28 0.299227 -0.812036 0.488411 +0.315439 0.000105 39 39 BCP39 C28-H29 0.280761 -0.988600 0.022208 +0.281177 0.000073 40 40 BCP40 C28-C30 0.304601 -1.061286 0.036974 +0.324759 0.000139 41 41 BCP41 C30-C32 0.304935 -0.871338 0.514585 +0.326585 0.000119

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Experimental IR Spectral Data and Calculated Frequencies

ATR-FTIR analysis of compound (pS)-3 revealed two strong and broad absorption bands at 2403 and 2378 cm-1 corresponding to the B‒H stretching frequencies. These bands are significantly shifted to 2417 and 2314 cm-1 in the IR spectrum of (pS)-4. DFT frequency calculations of the optimized structures predict absorption bands for 3 at 2462, 2524, and 2538 cm-1; and for (pS)-4 at 2443, 2505 and 2546 cm-1. According to the computed results, the B‒H stretching frequencies involved in an agostic-type interaction with the tin atom are assigned to be those at 2538 ((pS)-3) and 2443 ((pS)-4) cm-1, which suggests a bathochromic shift of 95 cm-1 that is similar to the bathochromic shift (89 cm-1) when comparing the experimentally observed bands at 2403 cm-1 in (pS)-3 and 2314 cm-1 in (pS)-4. The ATR-FTIR spectra of the parent compound FcPPh2·BH3 showed a broad absorption band at 2380 cm-1.

S41

Calculated Frequencies for Compound (pS)-3: Frequencies -- 2461.5186 2523.5996 2538.2687 Red. masses -- 1.0279 1.1106 1.1117 Frc consts -- 3.6695 4.1673 4.2202 IR Inten -- 44.7466 160.6705 139.2541

Atom AN X Y Z X Y Z X Y Z 4 5 0 -0.01 -0.04 -0.09 -0.05 -0.02 -0.05 0.09 -0.02 5 1 -0.36 0.31 -0.03 0.25 -0.23 0.01 0.62 -0.52 0.03 6 1 0.54 0.25 0.35 0.54 0.25 0.38 0.08 0.05 0.05 7 1 -0.15 -0.5 0.15 0.16 0.56 -0.19 -0.17 -0.52 0.17

Calculated Frequencies for Compound (pS)-4: Frequencies -- 2442.6894 2505.4818 2545.7510 Red. masses -- 1.0442 1.0872 1.1146 Frc consts -- 3.6709 4.0209 4.2561 IR Inten -- 197.7806 163.3441 118.9582

Atom AN X Y Z X Y Z X Y Z 5 5 -0.05 0.03 0.01 0.06 -0.04 0.06 -0.05 -0.09 -0.01 6 1 0.73 -0.5 0.14 -0.34 0.23 -0.05 -0.03 0 0 7 1 -0.22 -0.15 -0.17 -0.44 -0.35 -0.38 0.44 0.32 0.38 8 1 0.06 0.29 -0.1 0.15 0.55 -0.2 0.16 0.68 -0.26

S42

References:

1. M. A. Bennet, M. Contel, D. C. R. Hockless, L. L. Welling, A. C. Willis, Inorg. Chem.

2002, 41, 844-855.

2. The following van der Waals radii are used: H 1.10, B 1.92, O 1.52, P 1.80, Cl 1.75, Sn

2.17, Hg 2.05 Å; see M. Mantina, A. C. Chamberlin, R. Valero, C. J. Cramer, D. G.

Truhlar J. Phys. Chem. A, 2009, 113, 5806-5812; the value of 2.05 Å for Hg is taken

from S. S. Batsanov, J. Mol. Struct. 1999, 468, 151-159.

esi fcpsnphg bh3 rev finals28 600 figure s37.maldi-tof mass spectrum of rac-5; the additional peaks...

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