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Preparation, characterization, and structural systematics of diphosphane and diarsane complexes of indium(III) halides

Preparation, characterization, and structural systematics of diphosphane and diarsane complexes of indium(III) halides
Preparation, characterization, and structural systematics of diphosphane and diarsane complexes of indium(III) halides
The ligands o-C6H4(PMe2)2 and o-C6H4(AsMe2)2 (L?L) react with anhydrous InX3 (X = Cl, Br, or I) in a 2:1 InX3/ligand ratio to form [InX2(L?L)][InX4] containing distorted tetrahedral cations, established by X-ray crystal structures for L?L = o-C6H4(PMe2)2 (X = Br or I) and o-C6H4(AsMe2)2 (X = I). IR, Raman, and multinuclear NMR (1H, 31P, 115In) spectroscopy show that these are the only species present in solution in chlorocarbons and in the bulk solids. The products from reactions in a 1:1 or 1:2 molar ratio are more diverse and include the halide-bridged dimers [In2Cl6{o-C6H4(PMe2)2}2] and [In2X6{o-C6H4(AsMe2)2}2] (X = Cl or Br) and the distorted octahedral cation trans-[InBr2{o-C6H4(PMe2)2}2][InBr4]. The neutral complexes partially rearrange in chlorocarbon solution, with multinuclear NMR spectroscopy revealing [InX4]? among other species. The iodo complexes trans-[InI2(L?L)2][InI4(L?L)] contain rare examples of six-coordinate anions, as authenticated by an X-ray crystal structure for L?L = o-C6H4(PMe2)2. Two species of formula [In2Cl5(L?L)2]n[InCl4]n (L?L = o-C6H4(PMe2)2 and o-C6H4(AsMe2)2) were identified crystallographically and contain polymeric cations with six-coordinate indium centers bonded to one chelating L?L and a terminal chlorine, linked by alternating single and double chlorine bridges into chains. The complicated chemistry of InX3 with these two rigid chelates is contrasted with that of the flexible diphosphane Et2P(CH2)2PEt2, which forms [In2Cl6{Et2P(CH2)2PEt2}2], and with more sterically demanding o-C6H4(PPh2)2 (Sigl et al. Eur. J. Inorg. Chem. 1998, 203?210). The results also contrasted with those found for GaX3 with the same ligands
0020-1669
9691-9700
Cheng, Fei
a0339c70-2a78-4078-8845-62759ac926d3
Friend, Sarah I.
62cdc038-01cb-4b11-81d0-a13cd11a5f96
Hector, Andrew L.
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Cheng, Fei
a0339c70-2a78-4078-8845-62759ac926d3
Friend, Sarah I.
62cdc038-01cb-4b11-81d0-a13cd11a5f96
Hector, Andrew L.
f19a8f31-b37f-4474-b32a-b7cf05b9f0e5
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Webster, Michael
f26c6e36-cb2e-486e-b2ed-b0d25a3a71f7
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7

Cheng, Fei, Friend, Sarah I., Hector, Andrew L., Levason, William, Reid, Gillian, Webster, Michael and Zhang, Wenjian (2008) Preparation, characterization, and structural systematics of diphosphane and diarsane complexes of indium(III) halides. Inorganic Chemistry, 47 (20), 9691-9700. (doi:10.1021/ic801091n).

Record type: Article

Abstract

The ligands o-C6H4(PMe2)2 and o-C6H4(AsMe2)2 (L?L) react with anhydrous InX3 (X = Cl, Br, or I) in a 2:1 InX3/ligand ratio to form [InX2(L?L)][InX4] containing distorted tetrahedral cations, established by X-ray crystal structures for L?L = o-C6H4(PMe2)2 (X = Br or I) and o-C6H4(AsMe2)2 (X = I). IR, Raman, and multinuclear NMR (1H, 31P, 115In) spectroscopy show that these are the only species present in solution in chlorocarbons and in the bulk solids. The products from reactions in a 1:1 or 1:2 molar ratio are more diverse and include the halide-bridged dimers [In2Cl6{o-C6H4(PMe2)2}2] and [In2X6{o-C6H4(AsMe2)2}2] (X = Cl or Br) and the distorted octahedral cation trans-[InBr2{o-C6H4(PMe2)2}2][InBr4]. The neutral complexes partially rearrange in chlorocarbon solution, with multinuclear NMR spectroscopy revealing [InX4]? among other species. The iodo complexes trans-[InI2(L?L)2][InI4(L?L)] contain rare examples of six-coordinate anions, as authenticated by an X-ray crystal structure for L?L = o-C6H4(PMe2)2. Two species of formula [In2Cl5(L?L)2]n[InCl4]n (L?L = o-C6H4(PMe2)2 and o-C6H4(AsMe2)2) were identified crystallographically and contain polymeric cations with six-coordinate indium centers bonded to one chelating L?L and a terminal chlorine, linked by alternating single and double chlorine bridges into chains. The complicated chemistry of InX3 with these two rigid chelates is contrasted with that of the flexible diphosphane Et2P(CH2)2PEt2, which forms [In2Cl6{Et2P(CH2)2PEt2}2], and with more sterically demanding o-C6H4(PPh2)2 (Sigl et al. Eur. J. Inorg. Chem. 1998, 203?210). The results also contrasted with those found for GaX3 with the same ligands

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e-pub ahead of print date: 13 September 2008
Published date: 20 October 2008

Identifiers

Local EPrints ID: 145967
URI: https://eprints.soton.ac.uk/id/eprint/145967
ISSN: 0020-1669
PURE UUID: 3db04aa8-84fa-4b59-8cd3-4c0fddd8855a
ORCID for Andrew L. Hector: ORCID iD orcid.org/0000-0002-9964-2163
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 20 Apr 2010 08:25
Last modified: 20 Jul 2019 01:28

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