Some molecular rods: gold(I) complexes of 1,3-diynes. Crystal structures of Au(CCCCH)(PPh3) and {Cu3(μ-dppm)3}(μ3-I)(μ3-CCCCAuCCCCH)

Michael I. Bruce; Ben C. Hall; Brian W. Skelton; Mark E. Smith; Allan H. White

doi:10.1039/B107446F

Some molecular rods: gold(i) complexes of 1,3-diynes. Crystal structures of Au(CCCCH)(PPh₃) and {Cu₃(μ-dppm)₃}(μ₃-I)(μ₃-CCCCAuCCCCH)

Michael I. Bruce,*^a Ben C. Hall,^a Brian W. Skelton,^b Mark E. Smith^a and Allan H. White^b

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^a Department of Chemistry, Adelaide University, Adelaide, Australia
E-mail: michael.bruce@adelaide.edu.au

^b Department of Chemistry, University of Western Australia, Crawley, Australia

Abstract

Reaction of buta-1,3-diyne with AuCl(PPh₃) and (AuCl)₂(μ-dppm) in the presence of base gave the diynyl complexes Au(C [triple bond, length as m-dash] CCCH)(PPh₃) 1 and {Au(CCCCH)}₂(μ-dppm) 2, respectively. Similar reaction of W(CCCCH)(CO)₃Cp with the two gold(I) complexes gave the heteronuclear diyndiyls W{CCCC[Au(PPh₃]}(CO)₃Cp (known) and {Au(CCCC[W(CO)₃Cp])}₂(μ-dppm) 3. Reaction of [ppn][Au(acac)₂] with the appropriate diynes afforded [ppn][Au(C [triple bond, length as m-dash] CCCH)₂] 4, [ppn][Au{CCCC[W(CO)₃Cp]}₂] 5, [ppn][Au{CCCC[Au(PPh₃)]}₂] 6 and [ppn][Au(CCC₆H₄CCPh)₂] 7; the latter anion was also obtained as the very unstable NMe₄ salt. The reaction between 2 and {Au(OTf)}₂(μ-dppm) likely afforded cyclo-{Au₂(μ-C [triple bond, length as m-dash] CCC)(μ-dppm)}₂8, although this compound was not structurally characterised. On one occasion, the molecular rod {Cu₃(μ-dppm)₃}(μ₃-I)(μ₃-η¹-CCCCAuCCCCH) 9 was isolated and crystallographically characterised; a rational approach to 8 from [ppn][Au(CCCCH)₂] and [{Cu₃(μ-dppm)₃}(μ₃-I)₂]I gave instead the molecular dumbbell [{Cu₃(μ₃-I)(μ-dppm)₃}₂(μ₃:μ₃-C [triple bond, length as m-dash] CCCAuCCCC)]I 10.

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Article information

DOI: https://doi.org/10.1039/B107446F
Article type: Paper
Submitted: 16 Aug 2001
Accepted: 12 Dec 2001
First published: 11 Feb 2002

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J. Chem. Soc., Dalton Trans., 2002, 995-1001

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Some molecular rods: gold(I) complexes of 1,3-diynes. Crystal structures of Au(CCCCH)(PPh₃) and {Cu₃(μ-dppm)₃}(μ₃-I)(μ₃-CCCCAuCCCCH)

M. I. Bruce, B. C. Hall, B. W. Skelton, M. E. Smith and A. H. White, J. Chem. Soc., Dalton Trans., 2002, 995 DOI: 10.1039/B107446F

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Journal of the Chemical Society, Dalton Transactions