Reactions of R₂P–P(SiMe₃)Li with [(R′₃P)₂PtCl₂]. A general and efficient entry to phosphanylphosphinidene complexes of platinum. Syntheses and structures of [(η²-PPⁱPr₂)Pt(p-Tol₃P)₂], [(η²-PP^tBu₂)Pt(p-Tol₃P)₂], [{η²-PP(NⁱPr₂)₂}Pt(p-Tol₃P)₂] and [{(Et₂PhP)₂

Abstract

The reactions of lithium derivatives of diphosphanes R(2)P-P(SiMe(3))Li (R = (t)Bu, (i)Pr, Et(2)N and (i)Pr(2)N) with [(R'(3)P)(2)PtCl(2)] (R'(3)P = Et(3)P, Et(2)PhP, EtPh(2)P and p-Tol(3)P) proceed in a facile manner to afford side-on bonded phosphanylphosphinidene complexes of platinum [(eta(2)-P=R(2))Pt(PR'(3))(2)]. The related reactions of Ph(2)P-P(SiMe(3))Li with [(R'(3)P)(2)PtCl(2)] did not yield [(eta(2)-P=PPh(2))Pt(PR'(3))(2)] and resulted mainly in the formation of [{(R'(3)P)(2)Pt}(2)P(2)], Ph(2)P-PLi-PPh(2), (Me(3)Si)(2)PLi and (Me(3)Si)(3)P. Crystallographic data are reported for the compounds [(eta(2)-P=R(2))Pt(p-Tol(3)P)(2)] (R = (t)Bu, (i)Pr, ((i)Pr(2)N)(2)P) and for [{(Et(2)PhP)(2)Pt}(2)P(2)].

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

“…The still smaller coupling to the naked P atom ( 1 J PW = 48 Hz) is due to the fact that the P atom still carries a lone pair (with high s-character), and the PW bond is thus formally a σ-bond which exhibits a lower degree of s-character than a dative bond . Small P–M couplings to the naked phosphorus atom were also observed for phosphanylphosphinide Pt(0) complexes . Altogether, the 31 P NMR and X-ray data indicate that the bonding situation in 2 resembles that in [L 2 Pt­(η 2 - t -Bu 2 PP] (L = tertiary phosphine)…”

“…Our group develops the chemistry of phosphanylphosphinidenes (heavier analogues of aminophosphinidenes) and phosphanylphosphides, especially as ligands in transition metal chemistry. Altogether, we elaborated the synthesis of three types of compounds containing phosphanylphosphinidene groups (R 2 P–P): (a) relatively stable neutral, side-on complexes [L 2 Pt­(η 2 -R 2 PP)] (L = tertiary phosphine; R = t- Bu, i- Pr, i- Pr 2 N, Et 2 N) whose reactions with [(OC) 5 M·THF] (M = Cr, W) and t- Bu 2 P–PP­(Me) t Bu 2 suggest nucleophilic character of the R 2 P–P unit, (b) very reactive complexes [(Me 2 PhP)­Zr­(η 1 -P–P- t- Bu 2 )] and [Cp 2 Zr­{μ 2 -PP­(NEt 2 ) 2 } 2 ZrCp 2 ] with terminal and bridging R 2 P–P units, and (c) relatively stable anionic side-on complexes [(ArN) 2 (Cl)­Wη 2 -R 2 PP)] (Ar = 2,6- i- Pr 2 C 6 H 3 ; M = Mo and W; R = t- Bu and i- Pr). , Complexes that are related to group c were prepared by Cummins et al using nucleophilic terminal phosphide complexes of niobium Na­[(P)­Nb­{N­(3,5-Me 2 C 6 H 3 )­Np} 3 ] and tungsten [(P)­W­{N­(3,5-Me 2 C 6 H 3 ) i Pr} 3 ] as platforms for electrophilic phosphenium synthons. However, chemical properties of such complexes have not been investigated at all.…”

Solvent Impact on the Diversity of Products in the Reaction of Lithium Diphenylphosphide and a Ti(III) Complex Supported by a tBu2P–P(SiMe3) Ligand

“…Phosphanylphosphido complexes have been obtained for titanium, 37 − 39 iron, 18 hafnium, 40 zirconium, 40 − 42 tungsten, 43 and molybdenum, 44 and phosphanylphosphinidene complexes have been reported for titanium, 37 , 39 zirconium, 42 , 45 tungsten, 46 , 47 molybdenum, 48 and platinum. 49 − 52 Among these complexes, the complexes of titanium, zirconium, and iron were stabilized using a β-diketiminate ligand. The reactivity of the phosphanylphosphinidene complexes of tungsten was investigated by Grubba and co-workers.…”

Reactions of the Lithiated Diphosphine tBu2P–P(SiMe3)Li with [(η6‐C6H6)RuCl2]2 in the Presence of Tertiary Phosphines

“…The work described herein originated from our interest in providing new examples of phosphanylphosphido and phosphanylphosphinidene complexes by using R 2 P–P(SiMe 3 )Li as transfer reagents of R 2 P–P and R 2 P–P(SiMe 3 ) ligands. The lithium diphosphanides had previously proven very effective in the syntheses of phosphanylphosphinidene and phosphanylphosphido complexes of platinum, zirconium, hafnium,, tungsten,, and molybdenum , . Alternatively, splitting of the P–P bond in R 2 P–P(SiMe 3 ) 2 may occur to yield Pt 0 complexes featuring a P 2 ligand (see Scheme ).…”