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Heterometallic Boride Clusters: Formation of Octahedral (-)(M = Rh or Ir) and Gold(I) Phosphine Derivatives. Crystal Structures of , trans-> and cis->

DOI: 10.1039/DT9950000549

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 549 - 558 (1995)

Update date:2022-08-11

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Authors:

Galsworthy, Jane R.Galsworthy, Jane R.

Hattersley, Andrew D.Hattersley, Andrew D.

Housecroft, Catherine E.Housecroft, Catherine E.

Rheingold, Arnold L.Rheingold, Arnold L.

Waller, AnneWaller, Anne

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Article abstract of DOI:10.1039/DT9950000549

The reaction of the butterfly cluster (-) with led to the octahedral boride (-) 1.In solution, 11B NMR spectroscopic evidence supports the presence of both cis- and trans-isomers of 1.The trans form is predominant.When treated with >, 1 yielded > 3 in two isomeric forms 3a and 3b.Similar reactions occur with other phosphine gold(I) derivatives.The crystal structure of compound 3a has been determined and reveals a trans arrangement of Rh atoms and a face capping AuP(C6H11)3 unit.The anion (-) reacted with (L = cyclooctene or L2 = cycloocta-1,5-diene) under a stream of CO to give (-) 2; the crystal structure of 2 has been determined and confirms an octahedral metal framework with trans iridium atoms.Cluster 2 reacted with > to yield > 4 and crystallographic data for 4 show that the Ir atoms are mutually cis in the octahedral Ir2Ru4 skeleton.The AuP(C6H11)3 unit bridges the Ir-Ir edge.In (-), the four ruthenium atoms define a butterfly framework with the boron atom lying in a semi-interstitial position.The addition of two Group 9 metal atoms to close up the metal cage to an octahedral one with an M2Ru4 core should initially give a cis isomer.In fact the trans isomer is observed for both 1 and 2, although for 1 both cis and trans isomers are observed by 11B NMR spectroscopy.Geometrical preferences which accompany the addition of a gold(I) phosphine fragment to anions 1 and 2 to give 3 and 4 respectively are discussed.

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