Generation and reactivity of methylphosphaketene in the coordination sphere of tungsten

The [4 + 2] cycloadduct between the 1-methyl-2-keto-1,2-dihydrophosphinine pentacarbonyltungsten complex and dimethyl acetylenedicarboxylate can be used as a precursor for the methylphosphaketene tungsten complex under UV irradiation at room temperature. Under these conditions, the phosphaketene com...

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Bibliographic Details
Main Authors: Mao, Yanli, Wang, Zhiyue, Ganguly, Rakesh, Mathey, François
Other Authors: School of Physical and Mathematical Sciences
Format: Journal Article
Language:English
Published: 2013
Subjects:
Online Access:https://hdl.handle.net/10356/99720
http://hdl.handle.net/10220/13709
Description
Summary:The [4 + 2] cycloadduct between the 1-methyl-2-keto-1,2-dihydrophosphinine pentacarbonyltungsten complex and dimethyl acetylenedicarboxylate can be used as a precursor for the methylphosphaketene tungsten complex under UV irradiation at room temperature. Under these conditions, the phosphaketene complex easily loses CO to give the methylphosphinidene complex. Highly reactive alcohols and primary alkylamines trap both the phosphaketene and the phosphinidene complexes. Less reactive phenol and bulky amines together with alkynes and conjugated dienes only trap the phosphinidene complex.