Synthesis and Crystal Structure of the Nickel(II) Phosphoranide Complex trans-(PMe₃)₂[(C₄H₆O₃)₂P-P]NiCl

Formation of Iron−Fluorophosphorane Complexes (η5-C5H5)(CO)LFe{P(OPh)nF4-n} (L = CO, P(OPh)3; n = 0, 1) and (η5-C5H5)(CO)2Fe{P(OC6H4NMe)F2}. Nucleophilic Attack of F- toward a Trivalent Phosphorus Atom Coordinated to a Transition Metal

“…Trends for the Metallafluorophosphoranes in 31 P NMR Spectra. The 31 P NMR chemical shifts of the metallafluorophosphoranes reported here are reasonable when compared with those of the reported metallaphosphoranes having a Cp(CO)LFe fragment (L = CO, P(OPh) 3 , P(OMe) 3 , PMe 3 ). , In 2 and 4 , an apical P−F bond displays a smaller coupling constant than an equatorial P−F bond. The same trend is also observed in non-transition-metalated fluorophosphoranes and can be explained by the intrinsic difference in bond nature between apical and equatorial bonds.…”

“…They are based roughly on two strategies. One is based on reactions of a transition-metal complex with an organic phosphorane or a phosphoranide (a tetracoordinate anionic phosphorus compound). − Most of metallaphosphoranes reported so far have been prepared with recourse to this simple strategy. The other approach involves valence expansion of a lower-coordinate phosphorus ligand such as a phosphide or a phosphite ligand, coordinated to a transition metal, into a pentacoordinate phosphorus species by oxidative or nucleophilic addition of some inorganic or organic reagents to the phosphorus atom.…”

A New Method for the Formation of Anti‐apicophilic (O‐cis) Spirophosphoranes – Kinetic Studies on the Stereomutation of O‐cis Arylspirophosphoranes to Their O‐trans Isomers

“…Similar distortion has been found in a few phosphoranido complexes. [15] Additionally, the equatorial P-O bond of 2n (1.678 Å) was somewhat longer than those of alkyl derivatives 2b (1.658 Å) and 2c (1.652 Å), despite the apical P-O bond length of 2n (1.777 Å) being comparable to those of the alkyl derivatives 2b (1.773 Å) and 2c (1.771 Å). [7] Thus, the distortion from TBP geometry of 2n and 3n does not follow any pseudorotation process.…”

Metallophosphoranes: The hidden face of transition metal–phosphine complexes

“…The first crystallographically characterized metallophosphorane, 1, was reported by Riess and coworkers in 1981 [4] and a search of the Cambridge Structural Database now reveals more than 30 metallophosphoranes, including examples from Group 6 (Mo [5]), Group 7 (Mn [6]), Group 8 (Fe [7], Ru [8]), Group 9 (Co [9], Rh [10], Ir [11]) and Group 10 (Ni [12], Pd [13], Pt [10b,14]). The structures of metallophosphoranes generally fall into two cat- egories -a simple 1 -binding mode through phosphorus (as in 2 [6], 3 [10a] and 4 [11]) and a 2 -binding mode, where a heteroatom substituent on phosphorus can also donate to the metal centre (as in 1).…”