ISSN:
0009-2940
Keywords:
Methylenephosphanyl complexes
;
Phosphenium complexes
;
Phosphavinylidene complexes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Methylenephosphanyl Complexes of Chromium, Molybdenum, Tungsten, Iron and Nickel - Synthesis and ReactivityHerrn Professor Heinrich Nöth zum 65. Geburtstag gewidmet.The reaction of the functionalized P/C double bond systems X - P=C(R)SiMe3 [R=SiMe3 and X=Cl (1a), Cp* (5a) or R=Ph and X=Br (1b), Cp* (5b)] with alkali carbonylmetallates or carbonyl complexes of group 6, 8, and 10 metals leads to the formation of the transition metal-substituted phosphaalkenes [{M} - P=C(R)SiMe3 3a - j and 4a - i], in which the P - C fragment acts as a one-electron donor. Depending on the nucleophilicity of the transition metal anion used, but also on the methylene carbon substituents [1a: (SiMe3)2: 1b: (Ph)1-SiMe3], a different stability of the (methylenephosphanyl)1-metal complexes is observed, which results in a broad spectrum of reactivities. As demonstrated by the reactions of the (methylenephosphanyl)metal complexes with sulfonic acid derivatives (10a - c), diverse transition metal complexes (11a - c), as well as chalcogenes (14a - c, 15), a change in the reactivity is observed, indicating a transition from an olefinic to a carbenic character of the methylenephosphane. In comparison to the phenyl-substituted derivatives 4a - i the bis(trimethyl)1-substituted species 3a - j exhibit an increased reactivity. This is reflected in the easy decarbonylation of 3a - d to the phosphavinylidene complexes 12a - d.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19931260606
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