Cleavage of a phosphorus-carbon double bond and formation of a linear terminal phosphinidene complex

Nucleophilic Phosphinidene Complexes: Access and Applicability

“…Cowley et al [37] prepared tungsten phosphinidene [(MePh 2 P) 2 The groups of Mindiola and Protasiewicz jointly demonstrated that phospha-Wittig reagents of the type Me 3 P=PAr are effective as PAr transfer reagents for the synthesis of stable phosphinidene complexes.…”

Phospha‐Organic Chemistry: Panorama and Perspectives

“…The resulting terminal phosphinidene complexes exist in two types, as bent two-electron complexes [135] and as linear four-electron complexes. [136] Their reactivity can be tuned from nucleophilic to electrophilic by changing the ligands supporting the metal center from s donors to p acceptors (see, for example, the compounds 15-20). This effect has been studied in some depth in a recent DFT analysis.…”

“…The calculated tripletsinglet separations for RP, [151] the PÀW bond lengths in the corresponding [RPÀW(CO) 5 ] complexes, and the charges at phosphorus in these complexes [152,153] are given in Table 2. When the calculated PÀW bond lengths are compared with the experimental values found for P¼W (2.349(5) [135] ) and PW bonds (2.169(1) [136] ), it is quite clear that [RPÀ 5 Cr¼PH] using an electron localizing function (ELF) analysis led to the same conclusions: a Ti¼P double bond and negative charge at the phosphorus center in the former, a CrÀP single bond and positive charge at phosphorus in the latter. [154] Hence, [RPÀ M(CO) 5 ] species are best represented as Fischer-type phosphinidene complexes having a dative P!M single bond and a small contribution from p backdonation.…”

Terminal, Anionic Carbide, Nitride, and Phosphide Transition‐Metal Complexes as Synthetic Entries to Low‐Coordinate Phosphorus Derivatives

“…[53,54] Representative substituents on terminal phosphinidene ligands include Mes* (2,4,6-tBu 3 C 6 H 2 ), [55][56][57][58][59] 2,6-dimesitylphenyl (dmp), [60] cyclohexyl, [61] phenyl, [62] and trimethylsilyl. [63] An intriguing possibility was that the availability of a terminal phosphide anion, for example, [PNb(NNpAr) 3 ]…”