Phosphinidene group-transfer with a phospha-Wittig reagent: a new entry to transition metal phosphorus multiple bonds

Abstract

The phosphanylidene-sigma(4)-phosphorane reagents Me(3)P[double bond, length as m-dash]PAr (Ar = 2,4,6-(t)Bu(3)C(6)H(2) and 2,6-Mes(2)C(6)H(3)) are good delivery vehicles of the terminal phosphinidene moiety, PAr, to early-transition metals composed of zirconium and vanadium.

Metal–Ligand Multiple Bonding in Thorium Phosphorus and Thorium Arsenic Complexes

“…Through single crystal X-ray diffraction, we were able to characterize 3a in the solid state ( Figure 3). As expected, there is af our-coordinate tetrahedral geometry aroundt he metal center,w ith ThÀPb onds lengths of 2.6024(9)a nd 2.9677 (10) . Although the ThÀPs ingle bond shortenso nly by about 0.02 , the ThÀPd ouble bond length decreased more significantly,b y almost0 .1 from the bridging dimer.T he shortened bond length arises from the removal of the potassium ion from the monomeric unit upon its encapsulationi nt he 2,2,2-cryptand used in the reaction.…”

Synthesis and Structural Characterization of the First Thermally Stable, Neutral, and Electrophilic Phosphinidene Complexes of Vanadium

“…2,3 Transition metal-phosphinidene complexes are therefore analogous to better known metalcarbenes and imides. In fact, both nucleophilic phosphinidene complexes, [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] with an MdP double bond formally derived from the combination of triplet RP with a triplet ground state metal fragment, and electrophilic complexes [21][22][23][24][25][26] containing essentially M-Psingle bonds resulting from singlet RP-singlet metallic moieties are now well known. The chemistry of these two classes of molecules is now being intensively explored.…”

Iron‐ and Cobalt‐Catalyzed Synthesis of Carbene Phosphinidenes

“…TheI Me 4 / PhPH 2 control experiment at 80 8 8Cover three days produces a 31 PNMR spectrum dominated by unreacted phosphine and small amounts of 8,P 4 Ph 4 ,P 5 Ph 5 ,a nd P 2 H 2 Ph 2 (see Figures S50 and S51). Thereaction between IPr and PhPH 2 in the presence of [Fe(N'') 2 ]p roduced an approximately equimolar mixture of IPr, (IPr)·PPh (7), and IPr(H) 2 in addition to small amounts of P 2 H 2 Ph 2 (see Figures S42 and S43). TheI Pr/ PhPH 2 control experiment produced an 1 HNMR spectrum which consisted mainly of unreacted starting materials,w ith IPr, 7,a nd IPr(H) 2 being present in an approximate 5:1:1 ratio,a nd the 31 PNMR spectrum is dominated by unreacted PhPH 2 (see Figures S48 and S49).…”

“…[1][2][3][4][5] Complexes of the general type [L n M = PR] have been synthesized with many transition metals,and the ability of the phosphinidene ligand to display electrophilic or nucleophilic characteristics has enabled av ariety of phosphinidene-transfer reactions.W hile much of this chemistry was pioneered with 4d and 5d transition metals, [4,5] several important studies involving 3d metals have also been described. [6,7] Of particular significance is the three-coordinate nickel(II) phosphinidene complex [(dtbpe)Ni = P(C 6 H 3 -1,2-Mes 2 )] (dtbpe = di-tert-butylphosphinoethane,M es = mesityl), which is able to transfer the {PR} group to alkenes and alkynes in as toichiometric manner,t hus resulting in the formation of phosphorus heterocycles such as phosphiranes and phosphirenes. [6] Our interest in low-coordinate transition-metal chemistry has focused on iron and cobalt complexes of N-heterocyclic carbene (NHC) ligands.…”