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Abstract
Treatments of Mo- and Mn-diphosphite complexes, cis-Mo(CO)4L2 (1a) and CpMn(CO)L2 (2a) (L= P(NMeCH2)2(OMe)) with TMSOTf caused single OMe− abstraction from the coordinated phosphite to give the corresponding cationic phosphenium phosphite complexes cis-[Mo(CO)4LP(NMeCH2)2]OTf (1b) and [CpMn(CO)LP(NMeCH2)2]OTf (2b), respectively. DFT calculations for 1b and Cp(CO)2Mo(SiMe2)SiMe2(OMe) (3) revealed that a non-bridging form is a local minimum and a bridging form is a transition state for 1b, and both non-bridging and bridging forms are minima for 3.