Activation of arylnitroso substrates on a platinum-germylene complex facilitating the formation of new N-C and N-S bonds

Kyle E. Litz, Jeffrey W. Kampf, Mark M. Banaszak Holl

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Abstract

The reaction of (Et3P)2PtGe[N(SiMe2)2]2 (1) with nitrosobenzene and 2-nitrosotoluene yields (Et3P)2-PtN(Ph)OGe[N(siMe3)2]2 (3a) and (Et3P)2PtN(o-Tol)OGe[N(SiMe3)2]2 (3b), respectively. The reactivity of 3a with SO2, H2CO, CO2, and PhNCO was explored yielding the five-membered heterocyclic complex (Et3P)2- PtS(O)2N(Ph)OGe[N(SiMe3)2]2 (6a) and the six-membered heterocyclic complexes (Et3P)2PtOC(H)2N(Ph)OGe[N(SiMe3)2]2 (7a), (Et3P)2PtoC(O)N(Ph)OGe [N(SiMe3)2]2 (8a), and (Et3P)2PtN(Ph)C(O)N(Ph)C(O)N(Ph)OGe- [N(SiMe3)2]2 (9a), respectively. The structures of 3a, 6a, 7a, and 9a were determined by single-crystal X-ray diffraction. 3b was observed to react in a fashion similar to 3a as demonstrated by reactions with SO2 and H2CO which gave (Et3P)2PtS(O)2N(o-Tol)OGe[N(SiMe3)2]2 (6b) and (Et3P)2PtOC(H)2N(o-Tol)OGe[N(SiMe3)2]2 (7b). Complexes 6a and 6b represent the first isolated and characterized examples of metal-stabilized -S(O)2N-(R)O- fragments, the isoelectronic analogue of an elusive intermediate proposed as the first step in Contact Process for the oxidation of SO2 by platinum catalysts. As a group, the reactions in this paper demonstrate the cooperative ability of metal-germylenes to activate unsaturated organic substrates and promote their subsequent chemical modification, while avoiding scission of the Pt-Ge bond.

Original languageEnglish
Pages (from-to)7484-7492
Number of pages9
JournalJournal of the American Chemical Society
Volume120
Issue number30
DOIs
Publication statusPublished - 5 Aug 1998
Externally publishedYes

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