Issue 40, 2012

Variable coordination of a chiral diphosphine containing an amidinium/NHC group within its backbone: μ-P,P′, κ2-P,P′ and κ3-P,C,P′ coordination modes

Abstract

A diphosphine ligand (1·HPF66666), which is a potential precursor to a PCNHCP pincer, with a backbone containing two phenylene groups and a central bicyclic 4-aza-2-azoniabicyclo[3.2.1]oct-2-ene unit has been synthesised and coordinated to Pd(II) and Pt(II) to give trans-[M(κ2-P,P′-1·H)Cl2]PF6 where M = Pd (2) or Pt (3a). Single-crystal structure determinations of 2 and 3a show the complexes to be isostructural with the diphosphine coordinated in a trans-spanning fashion and the amidinium unit being protonated and non-coordinated. 2 and 3a react with CH3I to give the dimers trans-[Pd2(μ-1·H)2I4](PF6)2, 6, and trans-[Pt2(μ-1·H)2I4](PF6)2, 7, as the major products. This bridging mode of coordination of [1·H]+ is also seen in trans-[Rh2(μ-1·H)(1,5-COD)2Cl2]PF6, 4, and [Pt2(μ-κ2-1·H)(dvdms)]PF6, 5. Upon treatment with KOtBu complexes 2 and 3a undergo deprotonation at the amidinium carbon to give trans-[M(κ3-P,C,P′-1)Cl]PF6 where M = Pd (8), and Pt (9). The related trans-[Rh(κ3-P,C,P′-1)(CO)]PF6 (10) is prepared directly from 1·HPF66666 and Rh(acac)(CO)2: this and the palladium and platinum complexes 8 and 9 are isolated as isomeric mixtures as a consequence of a conformational isomerism. In situ deprotonation of 1·HPF66666 followed by addition of Ag(CF3SO3) gave SAg-[Ag(κ3-P,C,P′-1)(CF3SO3)], 11. Some preliminary studies of the reactivity of 2 and 8 in Suzuki-type reactions are reported and the Pt(0) system has been shown to be an active hydrosilylation catalyst.

Graphical abstract: Variable coordination of a chiral diphosphine containing an amidinium/NHC group within its backbone: μ-P,P′, κ2-P,P′ and κ3-P,C,P′ coordination modes

Supplementary files

Article information

Article type
Paper
Submitted
05 Jul 2012
Accepted
15 Aug 2012
First published
15 Aug 2012
This article is Open Access
Creative Commons BY license

Dalton Trans., 2012,41, 12395-12407

Variable coordination of a chiral diphosphine containing an amidinium/NHC group within its backbone: μ-P,P′, κ2-P,P′ and κ3-P,C,P′ coordination modes

P. D. Newman, K. J. Cavell and B. M. Kariuki, Dalton Trans., 2012, 41, 12395 DOI: 10.1039/C2DT31475D

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