Bhaduri, Sumit ; Grundy, Kevin ; Johnson, Brian F. G. (1977) Transition-metal nitrosyl compounds. Part 13. Some reactions of dinitrosylbis(triphenylphosphine)-cobalt, -rhodium, and -iridium cations Journal of the Chemical Society Dalton Transactions . pp. 2085-2091. ISSN 1472-7773
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Official URL: http://www.rsc.org/publishing/journals/DT/article....
Related URL: http://dx.doi.org/10.1039/DT9770002085
Abstract
The dinitrosyl cations [M(NO)2(PPh3)2]+(M = Co, Rh, or Ir) have been prepared and some of their reactions examined. A 31P n.m.r. study of the cations of Rh and Ir suggests that phosphine exchange is primarly via an associative process; evidence is also presented to suggest that exchange with the Co proceeds via a predominantly dissociative mechanism. Reaction of [Rh(NO)2(PPh3)2]+ or [Ir(NO)2(PPh3)2]+ with tertiary phosphines(L') gives [M(NO)(PPh3)3] and [NO]+when L'= PPh3 but [ML'4]+ when L'= a less bulky phosphine. In contrast, [Co(NO)2(PPh3)2][PF6] gives [Co(NO)2L2][PF6]. A rationale which accounts for this variation in reactivity is offered. The salt [Co(NO)2(PPh3)2][PF6] reacts with Cl-, Br-, or I-(X-) to provide [Co(NO)2(PPh3)X]; [Ir(NO)2(PPh3)2][PF6] reacts with HCl to form [Ir(NO)(PPh3)2Cl2]. Reaction of [Ir(NO)2(PPh3)2][PF6] with 2,2'-bipyridyl produces [Ir(NO)(PPh3)2(bipy)]2+ and N2O. Reduction of [M(NO)2(PPh3)2]+ by Na[BH4] in tetrahydrofuran and in the presence of PPh3 produces [M(NO)(PPh3)3] and ammonia.
| Item Type: | Article |
|---|---|
| Source: | Copyright of this article belongs to Royal Society of Chemistry. |
| ID Code: | 2170 |
| Deposited On: | 08 Oct 2010 07:40 |
| Last Modified: | 18 Jan 2011 08:16 |
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