Transformation of a Phosphorus-Bound Cp* Moiety in the Coordination Sphere of Manganese Carbonyl Complexes
Transformation of a Phosphorus-Bound Cp* Moiety in the Coordination Sphere of Manganese Carbonyl Complexes
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羰基锰配合物配位域中磷结合的 Cp* 部分的转化
DOI：
10.1021/om300808t
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发表时间：
2013
期刊：
影响因子：
2.8
通讯作者：
M. Scheer
中科院分区：
文献类型：
--
作者：
N. A. Pushkarevsky;S. N. Konchenko;A. V. Virovets;M. Scheer
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The reaction of Cp*PCl2with K[Mn(CO)5] yields two novel anionic products, [Mn2(CO)8(μ-PC11H14O)]−(1–) and [Mn2(CO)8(μ-PHCp*)]−(2–), instead of the expected phosphinidene complexes with a delocalized Mn–P–Mn bond system. By treating these anionic complexes with [Ph3PAuCl], they are converted into corresponding neutral derivatives [Mn2(CO)8(μ-PC11H14O)(μ-AuPPh3)] (3) and [Mn2(CO)8(μ-PHCp*)(μ-AuPPh3)] (4). NMR investigations and X-ray structural analyses for1–,3, and4show that the compounds1–and3as well as2–and4reveal similar molecular structures in which the neutral complexes3and4contain AuPPh3units bridging Mn–Mn bonds. In comparison to1and3, complexes2and4possess one additional H atom bound at the P atom. The structures of1and3include a novel bicyclic unit consisting of a C5ring of the former Cp* moiety conjugated to a CCC(O)P four-membered ring. The latter is built by a CO group of a former Mn carbonyl fragment connecting a P and a C atom of the cycle. One of the methyl groups of the Cp* ligand became a CH2unit, resulting in two isomers containing an exocyclic CH2moiety in the positions three or five of the C5ring. Both isomers were found in the reaction mixture, with one as the major isomer. The proposed reaction pathway is based on XRD, NMR, and MS data and includes the reduction of a transient [Cp*P(Mn(CO)5)2] complex by [Mn(CO)5]−, a proton transfer from the neutral to the reduced complex, and a successive reduction of the protonated species. The neutral bicyclic compound3, containing a 2-phosphacyclobutanone ring, is light sensitive and decomposes to tetramethylfulvene, possibly by a radical decarbonylation mechanism via a transient phosphacyclobutane derivative, [C5(CH3)4(CH2)P(Mn(CO)4)2AuPPh3] (5), detected by NMR spectroscopy.
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