Transition metal chloride complex

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Octahedral molecular geometry is a common structural motif for homoleptic metal chloride complexes. Examples include MCl6 (M = Mo, W), [MCl6]− (M = Nb, Ta, Mo, W, Re), [MCl6]2- (M = Ti Zr, Hf, Mo, Mn, Re, Ir, Pd, Pt), and [MCl6]3- (M = Ru Os, Rh, Ir).

In chemistry, a transition metal chloride complex is a coordination complex that consists of a transition metal coordinated to one or more chloride ligand. The class of complexes is extensive.[1]

Bonding[]

Halides are X-type ligands in coordination chemistry. They are both σ- and π-donors. Chloride is commonly found as both a terminal ligand and a bridging ligand. The halide ligands are weak field ligands. Due to a smaller crystal field splitting energy, the homoleptic halide complexes of the first transition series are all high spin. Only [CrCl6]3− is exchange inert.

Homoleptic metal halide complexes are known with several stoichiometries, but the main ones are the hexahalometallates and the tetrahalometallates. The hexahalides adopt octahedral coordination geometry, whereas the tetrahalides are usually tetrahedral. Square planar tetrahalides are known for Pd(II), Pt(II), and Au(III). Examples with 2- and 3-coordination are common for Au(I), Cu(I), and Ag(I).

Due to the presence of filled pπ orbitals, halide ligands on transition metals are able to reinforce π-backbonding onto a π-acid. They are also known to labilize cis-ligands.[2]

Homoleptic complexes[]

Homoleptic complexes (complexes with only chloride ligands) are often common reagents. Almost all examples are anions.

1st row[]

1st Transition Series
Complex colour electron config. structure geometry comments
TiCl4 colourless (t2g)0 Tetrahedral-tetrachlorometallate-3D-bs-20.png tetrahedral
[Ti2Cl9]− white/colourless d0d0 Face-shared-bioctahedral-nonachlorodimetallate-3D-bs-20.png face-sharing bioctahedron Ti-Cl(terminal) = 2.23 Å, 2.45 (terminal)
(N(PCl3)2)+ salt)[3]
[Ti2Cl9]3- orange (t2g)1(t2g)1 Face-shared-bioctahedral-nonachlorodimetallate-3D-bs-20.png face-sharing bioctahedron Ti-Ti =3.22 Å
Ti-C1(terminal) = 2.32-2.35 Å,
Ti-Cl(bridge) = 2.42-2.55 Å
((NEt4+)3)3 salt)[4]
[Ti2Cl10]2− colourless d0d0 Edge-shared-bioctahedral-decachlorodimetallate-3D-bs-20.png bioctahedral
[Ti3Cl12]3- green (t2g)1(t2g)1(t2g)1 Face-shared-trioctahedral-dodecachlorotrimetallate-3D-bs-20.png face-sharing trioctahedron Ti-Ti = 3.19, 3.10 Å (terminal)
Ti-C1(terminal) = 2.36 Å (terminal),
Ti-Cl(bridge) = 2.50 Å
((PPh4+)3)3 salt)[5]
[TiCl6]2− yellow d0 Octahedral-hexachlorometallate-3D-bs-20.png octahedral PPh4+ salt
Ti-Cl = 2.33 Å[6]
VCl4 red (t2g)1 Tetrahedral-tetrachlorometallate-3D-bs-20.png tetrahedral V1−Cl = 2.29 Å
V2Cl10 violet (t2g)0 Edge-shared-bioctahedral-decachlorodimetallate-3D-bs-20.png edge-shared bioctahedron V1−Cl(bridging) = 2.48 Å
V1−Cl(terminal) = 2.16-2.21 Å[7]
[VCl6]2- red (t2g)1 Octahedral-hexachlorometallate-3D-bs-20.png octahedral V1−Cl = 2.29 Å[8]
[CrCl6]3− ?? (t2g)3 Octahedral-hexachlorometallate-3D-bs-20.png octahedal[9]
[Cr2Cl9]3− red (d3)2 Face-shared-bioctahedral-nonachlorodimetallate-3D-bs-20.png face-sharing bioctahedron Cr-Cl(terminal) = 2.31 Å, 2.42 (terminal)
(Et2NH2+ salt)[10]
[MnCl4]2−[11] pale pink to while (eg)2(t2g)3 Tetrahedral-tetrachlorometallate-3D-bs-20.png tetrahedral Mn-Cl bond length = 2.3731-2.3830 Å[12]
[Mn2Cl6]2− yellow-green (eg)2(t2g)3 Bitetrahedral-hexachlorometallate-3D-bs-20.png bitetrahedral Mn-Cl(terminal) bond length = 2.24 Å
Mn-Cl(terminal) bond length = 2.39 Å[13]
(PPN+)2 salt
[MnCl6]2− dark red (t2g)3(eg)1 Octahedral-hexachlorometallate-3D-bs-20.png octahedral Mn-Cl distance = 2.28 Å
K+ salt[14])
salt is isostructural with K2PtCl6
[Mn3Cl12]6− pink (t2g)3(eg)2 Face-shared-trioctahedral-dodecachlorotrimetallate-3D-bs-20.png cofacial trioctahedron Mn-Cl distance = --- Å
[(C(NH2)3]+6 salt[15]
[FeCl4]2−[11] cream
((Et4N+)2 salt)[11] 		(eg)3(t2g)3 Tetrahedral-tetrachlorometallate-3D-bs-20.png tetrahedral
[FeCl4]− (eg)2(t2g)3 Tetrahedral-tetrachlorometallate-3D-bs-20.png tetrahedral Fe-Cl bond length = 2.19 Å[16]
[Fe2Cl6]2− pale yellow (eg)2(t2g)3 Bitetrahedral-hexachlorometallate-3D-bs-20.png bitetrahedral Fe-Cl(terminal) bond length = 2.24 Å
Fe-Cl(terminal) bond length = 2.39 Å[13]
(PPN+)2 salt
[CoCl4]2−[11] blue[11] (eg)4(t2g)3 Tetrahedral-tetrachlorometallate-3D-bs-20.png tetrahedral
[Co2Cl6]2− blue[13] (eg)4(t2g)3 Bitetrahedral-hexachlorometallate-3D-bs-20.png bitetrahedral Mn-Cl(terminal) bond length = 2.24 Å
Co-Cl(terminal) bond length = 2.35 Å[13]
(PPN+)2 salt
[NiCl4]2−[11] blue[11] (eg)4(t2g)4 Tetrahedral-tetrachlorometallate-3D-bs-20.png tetrahedral Ni-Cl bond length = 2.28 Å
(Et4N+)2 salt[17]
[Ni3Cl12]6− orange[18] (t2g)6(eg)2 Face-shared-trioctahedral-dodecachlorotrimetallate-3D-bs-20.png confacial trioctahedral ((Me2NH2+)2)8 salt
double salt with two Cl−
Ni-Cl bond length = 2.36-2.38 Å[18]
[CuCl4]2−[11] orange[19]
yellow (flattened tetrahedral)[20]
green (square planar)[21] 		(t2g)6(eg)3 Flattened-tetrahedral-tetrachlorometallate-3D-bs-20.png flattened tetrahedral
or square planar[22][23] 		Cu-Cl bond length = 2.24 Å
[Cu2Cl6]2− red [(t2g)6(eg)3]2 Edge-shared-bis-square-planar-hexachlorodimetallate-3D-bs-20.png edge-shared bis(square planar)[24] Cu-Cl(terminal) = 2.24 Å
Cu-Cl(bridging) = 2.31 Å
[ZnCl4]2− white/colorless d10 Tetrahedral-tetrachlorometallate-3D-bs-20.png tetrahedral

2nd row[]

Some homoleptic complexes of the second row transition metals feature metal-metal bonds.

2nd Transition Series
Complex colour electron config. structure geometry comments
[ZrCl6]2− yellow d0 Octahedral-hexachlorometallate-3D-bs-20.png octahedral Zr-Cl distance = 2.460 Å
(Me4N+)2 salt[26]
[Zr2Cl10]2− colorless (d0)2 Edge-shared-bioctahedral-decachlorodimetallate-3D-bs-20.png edge-shared bioctahedral Zr-Cl = 2.36 Å (terminal), 2.43 Å (bridging)
N(PCl3)2)+ salt[3]
Nb2Cl10 yellow (d0)2 Edge-shared-bioctahedral-decachlorodimetallate-3D-bs-20.png edge-shared bioctahedral [Nb2Cl10] 3.99 Å[27]
[NbCl6]− yellow d0 Octahedral-hexachlorometallate-3D-bs-20.png octahedral Nb-Cl = 2.34 Å
N(PCl3)2)+ salt[3]
[Nb6Cl18]2− black (d2)4(d3)2 (14 cluster electrons) Octahedral-octadecachlorohexametallate-3D-bs-20.png cluster Nb---Nb bonding Nb-Cl = 2.92 Å
(K+)2 salt[28]
MoCl6 black d0 Octahedral-hexachlorometallate-3D-bs-20.png octahedron Mo−Cl = 2.28 -2.31 Å[7]
[MoCl6]2− yellow (t2g)2 Octahedral-hexachlorometallate-3D-bs-20.png octahedron Mo−Cl = 2.37, 2.38, 2.27 Å[29]
[MoCl6]3− pink (t2g)3 Octahedral-hexachlorometallate-3D-bs-20.png octahedral
[Mo2Cl8]4− purple[30] 2(d4) Octachlorodimetallate-view-2-3D-bs-20.png Mo-Mo quadruple bond
[Mo2Cl9]3− 2(d3) Face-shared-bioctahedral-nonachlorodimetallate-3D-bs-20.png face-shared bioctahedral Mo-Mo (triple) bond length = 2.65 Å
Mo-Cl (terminal) bond length = 2.38 Å
Mo-Cl (bridging) bond length = 2.49 Å[31][32]
Mo2Cl10 green (d1)2 Edge-shared-bioctahedral-decachlorodimetallate-3D-bs-20.png edge-sharing bioctahedra[33]
[Mo2Cl10]2− (d2)2 Edge-shared-bioctahedral-decachlorodimetallate-3D-bs-20.png edge-sharing bioctahedra[34]
[Mo5Cl13]2− brown[30] d2d2d2d2d3 Tridecachloropentametallate-3D-bs-20.png incomplete octahedron[35]
[Mo6Cl14]2− yellow d4 Tetradecachlorohexametallate-3D-bs-20.png octahedral cluster (4-HOPyH+)2 salt[36]
[TcCl6]2− yellow (t2g)3 Octahedral-hexachlorometallate-3D-bs-20.png octahedron Tc-Cl = 2.35 Å for As(C6H5)4+ salt[37]
[Tc2Cl8]2− green (t2g)4 Octachlorodimetallate-view-2-3D-bs-20.png Tc-Tc quadruple bond Tc-Tc = 2.16, Tc-Cl = 2.34 Å for NBu4+ salt[38]
[RuCl6]2− brown (t2g)4 Octahedral-hexachlorometallate-3D-bs-20.png octahedral (EtPPh3+)2 salt[39]
[Ru2Cl9]3− red [(t2g)5]2 Face-shared-bioctahedral-nonachlorodimetallate-3D-bs-20.png cofacial bioctahedral Ru-Ru bond length = 2.71 Å; Ru-Cl(terminal) = 2.35 Å, Ru-Cl(bridging) = 2.36 Å ((Et4N)+)3 salt[40]
[Ru3Cl12]4− green (d5)2(d6) Face-shared-trioctahedral-dodecachlorotrimetallate-3D-bs-20.png cofacial trioctahedral Ru-Ru bond lengths = 2.86 Å
Ru-Cl bond lengths = 2.37-2.39 Å
(Et4N+)2(H7O3+)2 salt[41]
[RhCl6]3− red (t2g)6 Octahedral-hexachlorometallate-3D-bs-20.png octahedral H2N+(CH2CH2NH3+)2 salt)[42]
[Rh2Cl9]3− red-brown (t2g)6 Face-shared-bioctahedral-nonachlorodimetallate-3D-bs-20.png octahedral Rh-Cl(terminal) = 2.30 Å, Rh-Cl(terminal) = 2.40 Å
((Me3CH2Ph)+)3 salt)[31]
[PdCl4]2− brown d8 Square-planar-tetrachlorometallate-view-3-3D-bs-20.png square planar
[Pd2Cl6]2−[43] red ((Et4N+)2 salt) d8 Edge-shared-bis-square-planar-hexachlorodimetallate-3D-bs-20.png square planar
[Pd3Cl8]2−[44] orange brown ((Bu4N+)2 salt) d8 Octachlorotrimetallate-3D-bs-20.png square planar
[PdCl6]2− brown d6 Octahedral-hexachlorometallate-3D-bs-20.png octahedral Pd(IV)
[Pd6Cl12] yellow-brown d8 Dodecachlorohexametallate-3D-bs-20.png square planar[45]
[AgCl2]− white/colorless d10 Linear-dichlorometallate-3D-bs-20.png linear salt of [K(2.2.2-crypt)]+[46]
[CdCl4]2− white/colorless d10 Tetrahedral-tetrachlorometallate-3D-bs-20.png tetrahedral Et4N+ salt, Cd-Cl distance is 2.43 Å[25]
[Cd2Cl6]2− white/colorless d10 Bitetrahedral-hexachlorometallate-3D-bs-20.png edge-shared bitetrahedron (C6N3(4-C5H4N)33+ salt[47]
[Cd3Cl12]6− white/colorless d10 Face-shared-trioctahedral-dodecachlorotrimetallate-3D-bs-20.png octahedral (central Cd)
pentacoordinate (terminal Cd's)
cofactial trioctahedral 		(C6N3(4-C5H4N)33+ salt[47]
(3,8-Diammonium-6-phenylphenanthridine3+)2[48]
[Cd6Cl19]7− white/colorless d10 Octahedral-nonadecachlorohexametallate-3D-bs-20.png octahedron of octahedra 4,4'-(C6H3(2-Et)NH3+)2 salt[49]

3rd row[]

3rd Transition Series
Complex colour electron config. structure geometry comments
[HfCl6]2− white d0 Octahedral-hexachlorometallate-3D-bs-20.png octahedral Hf-Cl distance = 2.448 A
((Me4N+)2 salt)[26]
[Hf2Cl10]2− colorless/white d0 Edge-shared-bioctahedral-decachlorodimetallate-3D-bs-20.png edge-shared bioctahedral[50]
[Hf2Cl9]− colorless/white (d0)2 Face-shared-bioctahedral-nonachlorodimetallate-3D-bs-20.png face-shared bioctahedral[51]
[TaCl5] white d0 Edge-shared-bioctahedral-decachlorodimetallate-3D-bs-20.png edge-shared bioctahedral
[TaCl6]− white/colourless d0 Octahedral-hexachlorometallate-3D-bs-20.png octahedral Ta-Cl = 2.34 Å
(N(PCl3)2)+ salt)[3]
[Ta6Cl18]2- green d0 Octahedral-hexachlorometallate-3D-bs-20.png octahedral Ta-Ta = 2.34 Å
(H+2 salt hexahydrate[52]
WCl6 blue d0 Octahedral-hexachlorometallate-3D-bs-20.png octahedral 2.24–2.26 Å[53]
[WCl6]2− (t2g)2 Octahedral-hexachlorometallate-3D-bs-20.png octahedral W-Cl distances range from 2.34 to 2.37 Å
(PPh4+ salt)[54]
[WCl6]− (t2g)1 Octahedral-hexachlorometallate-3D-bs-20.png octahedral W-Cl distance = 2.32 Å
(Et4N+ salt)[55]
W2Cl10 black[56] (t2g1)2 Edge-shared-bioctahedral-decachlorodimetallate-3D-bs-20.png bioctahedral W-W distance = 3.814 Å[57]
[W2Cl8]4− blue 2(d4) Octachlorodimetallate-view-2-3D-bs-20.png W-W quadruple bond dW-W = 2.259 Å [Na(tmeda)+]4 salt[58]
[W2Cl9]2− d3d2 Face-shared-bioctahedral-nonachlorodimetallate-3D-bs-20.png face-sharing bioctahedral W-W distance = 2.54 Å
W-Cl(terminal) = 2.36 Å, W-Cl(bridge) = 2.45 Å
((PPN+)2 salt)[59]
[W2Cl9]3− d3d3 Face-shared-bioctahedral-nonachlorodimetallate-3D-bs-20.png octahedral W-Cl distance = 2.32 Å
(Et4N+ salt)[59]
[W3Cl13]3− d3,d3,d4 Tridecachlorotrimetallate-3D-bs-20.png [W3(μ3-Cl)(μ-Cl)3Cl9]3- W-W distances = 2.84 Å[60]
[W3Cl13]2− d3,d4,d4 Tridecachlorotrimetallate-3D-bs-20.png [W3(μ3-Cl)(μ-Cl)3Cl9]2-[60] W-W distances = 2.78 Å[60]
[W6Cl14]2- yellow[61] (d4)6 Tetradecachlorohexametallate-3D-bs-20.png see Mo6Cl12
[ReCl6]− red-brown (t2g)6 Octahedral-hexachlorometallate-3D-bs-20.png octahedral Re-Cl distance = 2.24-2.31 Å
(PPh4+ salt)[62]
[ReCl6] (t2g)1 Octahedral-hexachlorometallate-3D-bs-20.png octahedral Re-Cl distance = 226.3(6) Å[7]
[ReCl6]2− green (t2g)5 Octahedral-hexachlorometallate-3D-bs-20.png octahedral Re-Cl distance = 2.35-2.38 Å
((PPN+)2 salt)[63]
[Re2Cl9]2− (t2g)5 Face-shared-bioctahedral-nonachlorodimetallate-3D-bs-20.png face-sharing bioctahedral Re-Re distance = 2.48 Å
Re-Cl distances = 2.42 Å (bridge), 2.33 Å (terminal)
((Et4N+)2 salt)[64]
[Re2Cl9]− (t2g)5 Face-shared-bioctahedral-nonachlorodimetallate-3D-bs-20.png face-sharing bioctahedral Re-Re distance = 2.70 Å
Re-Cl distances = 2.41 (bridge), 2.28 Å (terminal)
(Bu4N+ salt)[64]
[OsCl6]− dark green (t2g)5 Octahedral-hexachlorometallate-3D-bs-20.png octahedral dOs-Cl = 2.30 Å for Et4N+[65] and Ph4P+[66] salts
[OsCl6]2− yellow-orange (t2g)4 Octahedral-hexachlorometallate-3D-bs-20.png octahedral[66] Os-Cl distance 2.33 Å
[Os2Cl8]2− green (d5)2 Square-antiprismatic-octachlorodimetallate-view-2-3D-bs-20.png square antiprism dOs-Os = 2.182 Å, dOs-Cl = 2.32 Å (Bu4N+)2 salt[67]
[Os2Cl10]2− green (d4)2 Edge-shared-bioctahedral-decachlorodimetallate-3D-bs-20.png octahedral dOs-Cl(terminal) = 2.30 Å dOs-Cl(bridging) = 2.42 Å (Et4N+)2 salt[65]
[IrCl6]3− red (t2g)6 Octahedral-hexachlorometallate-3D-bs-20.png octahedral Ir-Cl = 2.36 Å[68]
[IrCl6]2− brown (t2g)5 Octahedral-hexachlorometallate-3D-bs-20.png octahedral Ir-Cl = 2.33 Å[69]
[Ir2Cl9]3− brown (t2g)6 Face-shared-bioctahedral-nonachlorodimetallate-3D-bs-20.png bi-octahedral[70]
[PtCl4]2− pink d8 Square-planar-tetrachlorometallate-view-3-3D-bs-20.png square planar
[PtCl6]2− yellow d6 Octahedral-hexachlorometallate-3D-bs-20.png octahedral Pt-Cl distance = 2.32 Å
Et4N+ salt, ((Me4N+)2 salt)[26]
[Pt2Cl9]− red (Bu4N+ salt) (t2g)6 Face-shared-bioctahedral-nonachlorodimetallate-3D-bs-20.png octahedral Pt-Clt and Pt-Clbridge = 2.25, 2.38 Å[70]
[Pt6Cl12] yellow-brown d8 Dodecachlorohexametallate-3D-bs-20.png square planar Pt-Cl = 2.31[71]
[AuCl2]− white/colorless d10 Linear-dichlorometallate-3D-bs-20.png linear Au-Cl distances of 2.28 Å
NEt4+ salt[72]
[AuCl4]− yellow d8 Square-planar-tetrachlorometallate-view-3-3D-bs-20.png square planar Au-Cl distances of 2.26 Å
NBu4+ salt[73]
[HgCl4]2− white/colorless d10 Tetrahedral-tetrachlorometallate-3D-bs-20.png tetrahedral Hg-Cl distance is 2.46 Å[25]
Et4N+ salt
[Hg2Cl6]2− white/colorless d10 Bitetrahedral-hexachlorometallate-3D-bs-20.png edge-shared bitetrahedral Hg-Cl distance is 2.46 Å[74]
Bu4N+ salt

Heteroleptic complexes[]

Heteroleptic complexes containing chloride are numerous. Most hydrated metal halides are members of this class. Hexamminecobalt(III) chloride and Cisplatin (cis-Pt(NH3)2Cl2) are prominent examples of metal-ammine-chlorides.

Hydrates[]

"Nickel dichloride hexahydrate" consists of the chloride complex trans-[NiCl2(H2O)4 plus water of crystallization.

As indicated in the table below, many hydrates of metal chlorides are molecular complexes.[75][76] These compounds are often important commercial sources of transition metal chlorides. Several hydrated metal chlorides are not molecular and thus are not included in this tabulation. For example the dihydrates of manganese(II) chloride, nickel(II) chloride, copper(II) chloride, iron(II) chloride, and cobalt(II) chloride are coordination polymers.

Formula of
hydrated metal halides		 Coordination
sphere of the metal
TiCl3(H2O)6 trans-[TiCl2(H2O)4]+[77]
VCl3(H2O)6 trans-[VCl2(H2O)4]+[77]
CrCl3(H2O)6 trans-[CrCl2(H2O)4]+
CrCl3(H2O)6 [CrCl(H2O)5]2+
CrCl2(H2O)4 trans-[CrCl2(H2O)4]
CrCl3(H2O)6 [Cr(H2O)6]3+[78]
MnCl2(H2O)6 trans-[MnCl2(H2O)4]
MnCl2(H2O)4 cis-[MnCl2(H2O)4][79]
FeCl2(H2O)6 trans-[FeCl2(H2O)4]
FeCl2(H2O)4 trans-[FeCl2(H2O)4]
FeCl3(H2O)6 one of four hydrates of ferric chloride,[80]
FeCl3(H2O)2.5 cis-[FeCl2(H2O)4]+[81]
CoCl2(H2O)6 trans-[CoCl2(H2O)4]
CoCl2(H2O)4 cis-[CoCl2(H2O)4]
NiCl2(H2O)6 trans-[NiCl2(H2O)4]
NiCl2(H2O)4 cis-[NiCl2(H2O)4]

Ether complexes[]

Metal chlorides form adducts with ethers, especially tetrahydrofuran[82] and chelating ethers. These compounds are often important reagents because they are soluble and anhydrous.

Formula of
Metal-Chloride-eher Complexes		 Coordination
sphere of the metal		 color
TiCl4(thf)2 TiO2Cl4 yellow [83]
TiCl3(thf)3 TiO3Cl3 blue
[TiCl3(thf)2]2 TiO2Cl4 green[84]
ZrCl4(thf)2 ZrO2Cl4 white
HfCl4(thf)2 HfO2Cl4 white
VCl3(thf)3 VO3Cl3 pink
[VCl3(thf)2]2 VO2Cl4 red[85]
NbCl4(thf)2 NbO2Cl4 yellow
Ta3Cl9(thf)4 TaO2Cl4 and TaOCl5[86]
CrCl3(thf)3 CrO3Cl3 pink
MoCl4(thf)2 MoO2Cl4 pink[87]
MoCl3(thf)3 MoO3Cl3 red[87]
MnO3Cl3 brown-purple[88]
TcCl4(thf)2 TcO2Cl4 yellow[89]
ReCl4(thf)2 ReO2Cl4 green[90]
Fe4Cl8(thf)6 FeO2Cl3, FeO2Cl4 brown[91]
Co4Cl8(thf)6 CoO2Cl3, CoO2Cl4 blue[92]
NiCl2(dimethoxyethane)2 NiCl2O4 yellow[93]
[Cu2Cl4(thf)3]n CuO2Cl4, CuOCl4 orange[94]

References[]

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