Reactions of Lithium Salts of Triphosphanes tBu₂P–PLi–PtBu₂ and tBu₂P–PLi–P(NEt₂)₂ with Metal Complexes [(R₃P)₂MCl₂] (M = Ni, Pd, Pt, R₃P = Et₃P, pTol₃P, Ph₂EtP, iPr₃P)

Abstract

tBu 2 P-PLi-PtBu 2 ·2THF reacts with [(R 3 P) 2 MCl 2 ] (M = Pt, Pd, Ni; R 3 P = Et 3 P, pTol 3 P, Ph 2 EtP, iPr 3 P) to yield isomers of [(1,2-η-tBu 2 P=P-PtBu 2 )M(PR 3 )Cl], in which the tBu 2 P-P-PtBu 2 ligand adopts the arrangement of a side-on bonded 1,1-di-tert-butyl-2-(di-tert-butyl-* Prof. Dr. J. Pikies E-Mail: jerzy.pikies@pg.gda.pl [a] 1549 phosphanyl)diphosphenium cation. tBu 2 P-PLi-P(NEt 2 ) 2 ·2THF reacts with [(R 3 P) 2 MCl 2 ] but does not form complexes with a tBu 2 P-P-P(NEt 2 ) 2 moiety, however, splitting of a P-P(NEt 2 ) 2 bond of the parent triphosphane takes place.

Bonding in Phosphanylphosphinidene Complexes of Transition Metals and their Correlation with Structures, 31P NMR Spectra, and Reactivities

“…Moreover, side‐on bonded phosphanylphosphinidene complexes of platinum differ substantially from the ones of earlier transition metals , . Similar properties are observed for complexes with diphosphanylphosphido ligands (R 2 P–P–PR 2 ) , . Thus, these modes of bonding are of general importance and have hitherto not been discussed sufficiently in the literature.…”

Reactivity of Phosphanylphosphinidene Complex of Tungsten(VI) toward Phosphines: A New Method of Synthesis of catena-Polyphosphorus Ligands

“…A ruthenium complex with a P­(OH) 2 PHPHPH­(OH) ligand was synthesized via a hydrolysis reaction of complexed P 4 molecules . As precursors of catena -polyphosphido ligands in syntheses of the transition metal complexes, di- , and triphosphanides , or tetraphosphane-diides , were used. Several catena -polyphosphido complexes were synthesized via cleavage of a P–P bond in cyclophosphines, or the cyclo-P 5 unit of the ferrocene analogue [Cp*FeP 5 ] which occurs when the phosphorus substrates react with transition metal fragments.…”

Synthetic, Structural, and Spectroscopic Characterization of a Novel Family of High-Spin Iron(II) [(β-Diketiminate)(phosphanylphosphido)] Complexes

“…49 We have discussed the geometries of these nonclassical phosphido ligands in terms of a η 2 -bonded diphosphenium cation. 48 3.2.2. Crystal Structure of 3.…”

“…47 One striking structural feature of 2 is embodied by the short P1−P2 distance of 2.168(2) Å, suggesting a partial double-bond character of the P−P bond. Similar bond lengths were previously linked by us to η 2coordination mode of the t-Bu 2 PPP-t-Bu 2 moiety in [(η 2 -R 2 PPPR 2 )M(Cl)L] (2.12−2.16 Å; L = tertiary phosphine; M = Ni, Pd, Pt) 48 and in [(η 2 -t-Bu 2 PPP-t-Bu 2 )M(2,6-i-Pr 2 C 6 H 3 N) 2 Cl] (2.15−2.16 Å; M = Mo, W). 49 We have discussed the geometries of these nonclassical phosphido ligands in terms of a η 2 -bonded diphosphenium cation.…”