1

Chapter 22 d-block metal chemistry:

the second and third row metals

Occurrence, extraction, and uses

Physical properties

Inorganic Chemistry

2

Relative abundances of the second and third row d-block metals in the Earth’s crust. The data are plotted on a logarithmic scale, and the units of abundance are parts per 10

3

Trends in the values of standard enthalpies of atomization (298 K)

4

yttriumY2O3 YX3 (X = F, Cl, Br, I) Y3+ + 3e- ⇌ Y E° = -2.37 V

C.N. = 9

Coordination compounds C.N. = 6 to 9

YCl3 + 3KCl → K3YCl6

YBa2Cu3O7-x Superconductor

dodecahedral ion [Y(OH2)8]3

zirconium and hafnium

C.N. = 8

[Zr4(OH)8(OH2)16]8

MCl4, MO2: Extended solids w/chains of edge sharing-octahedra or related structures

Cubic zirconia

HfF4 + 3 KF K3[HfF7]∆ in sealed Pt tube

Hf + HfCl4 HfCl1070 K in sealed Ta tube

Hf + HfCl4 HfCl3720 K in sealed Ta tube

(unbalanced)

(unbalanced)

Lower oxidation states of hafnium

5

Zr(acac)4

monocapped trigonal prismatic

[ZrF7]3-

[ZrF7]3-

pentagonal bipyramidal

[H3N(CH2)2NH2(CH2)2NH3][ZrF7]

square antiprismatic

in a guanidinium salt

ZrCl4 + 2N2O5 → [Zr(NO3-O,O’)4] + 4NO2Cl

dodecahedral

[Zr6Cl14(PnPr3)4)] [Zr5Cl12(m-H)(m-H)2(PMe3)5]

m-H and m3-H are present in the Zr5 framework

Zirconium clusters

6

niobium and tantalum

The linearity of the bridge indicates multiple bond character.

[Ta2OF10]2-

M2O5 (M = Nb, Ta)

MX5 (M = Nb, Ta; X = F, Cl, Br, I)

NbOCl3

The structure of [Nb(OH2)(O)F4]- illustrates how oxo and aqua ligand O atoms can be distinguished.• The Nb-F bonds bend away from the oxido O=Nb bond• Difficult to locate H atoms using XRD

Niobium(V) and tantalum(V) have a variety of coordination environments:trigonal bipyramidal: [Ta(NEt2)5]

square-based pyramidal: [NbOCl4]-

octahedral: [Nb(OH2)(O)(F4)]-

pentagonal bipyramidal: [Nb(OH2)2(O)(ox)2]-

capped trigonal prismatic: K2[MF7] (M = Nb, Ta)

dodecahedral: [M(η2-O2)2F4]3- (M = Nb, Ta)square antiprismatic: Na3[MF8] (M = Nb, Ta)

7

niobium(IV) and tantalum(IV)

shortNb-Nb

shortNb-Nb

longNb-Nb

[Nb6I8]3+[M6X12]n+ (n=2 or 3)

3d 2d

8

[Nb6Cl18]3-Part of solid state structure of Nb3Cl8

molybdenum and tungsten

MoOF4 WOF4

infinite chains tetrameric units

9

[Mo7O24]6- [W6O19]2-

• Common structural features: cage is supported by oxygen bridges and there is no metal-metal bonding

• Cage is constructed from octahedral MoO6-units connected by shared oxygen atoms.

[SiMo12O40]4- [H3S2Mo18O62]5

-Keggin anion -Dawson anion

10

-form of MoCl4 consists of cyclic Mo6Cl24 units [Mo3(m3-O)(m-O)3(OH2)9]4

W6Cl18

11

Mo2(NMe2)6 Mo2Cl2(NMe2)4 Mo2(OCH2tBu)6

[Mo6Cl14]2 W6Cl18C [Mo2Cl8]4

12

technetium and rhenium pH 0

Re3Cl9 [Re3Cl12]3

13

two polymorphs of OsOF4

14

adduct formed between N-methylmorpholineand OsO4

[Os2(NtBu)4(m-NtBu)2]2

[OsO2(O2CMe)3]

ruthenium and osmium

Partial MO diagram for the interaction between the dxy, dxz and dyz atomic orbitals of the Ru(IV) centers

15

Representative complex-forming reactions starting from [OsCl6]2

[Os2Cl8]2-

staggered eclipsed

16

[HIm][trans-RuCl4(Im)(DMSO-S)]

[HInd][trans-RuCl4(Ind)2]

(Im imidazole, Ind indazole)

[RuBr3(Et2S)(Et2SO)(NO)] [RuCl(NO)2(PPh3)2]

17

rhodium and iridium

18

[Ir(NCS-S)6]3 [Ir(S6)3]3

[Rh2(m-O2CR)4] [Rh2(m-O2CR)4L2]

[Rh2(m-O2CMe)4(OH2)2]

19

palladium and platinum

PtCl2 --(F2, 620 K) PtF5

-red solidPtF5 disproportionates into PtF4 and PtF6

Platinum blues – mixed valent complexes containing discrete Ptn chains• {Pt4}9+ complex

Tetrameric structure of PtF5

X- CN- I- Br- Cl-

v(Pt-H) (cm-1) 2041 2156 2178 2183 (1H for Pt-H), ppm -7.8 -12.7 -15.6 -16.8

trans-influence

20

copper and silver

silver and gold

Part of one chain in the solid state structure of AuSO4, which contains [Au2]4 units; the [SO4]2 act as both bridging and monodentate ligands

[AuL2]2 (L1,4,7-trithiacyclononane)

21

[Au2(H2NCH2CH2NHCH2CH2NH2)2]2+ (part of one chain in which dimers are connected by weak AuAu interactions is shown)

trimer [Ag3L3]3 where L is the sulfur-containing macrocycle1,4,7-trithiacyclononane

[Au2(CS3)2]2 [Au2(TeS3)2]2

cadmium and mercury

Solubilities of Hg(II) halides in water