Platinum group metal functionalized phosphine complexes. Part 1: Phosphinoamide ruthenium(II) complexes

Abstract

Functionalized phosphine Pt complexes 1. 283 complexes. Summary Three new bifunctional phosphinoamide ligands of the type Ph2PCH2C(O)NHR (R = H, HDPA; Me, MDPA; Ph, PDPA) were prepared and characterized. Their ruthenium(II) complexes prepared from two different precursors, RuC12-(DMSO)4 and RuClz(PPh3) 3, are of similar composition and correspond to the formula, [RuCI(L)2(P O)2]C1 (L-DMSO/PPh3; phosphinoamide). However, RuC13-(AsPh3)2(MeOH) reacts with the phosphinoamide to yield a reduced product of the cis-RuClz(P--O)z type.The tigands and complexes were characterized by mass, i.r. and n.m.r, spectroscopy. Possible stereochemistries for the complexes are proposed.

Chemoselective Reactions of the Phosphino Enolate Li[Ph2PCH C( O)NPh2] with Ph2P−Cl and M−Cl Bonds (M = Pd, Pt). Coordination Properties of the New Functional Diphosphine Ligand (Ph2P)2CHC(O)NPh2. Hemilabile Behavior of [Cu2{(Ph2P)2CHC(O)NPh2-P,P,O}2](BF4)2. Reactivity and Molecular Structure of [(8-mq)Pd{Ph2PCH C( O)NPh2

“…Enolates are known to be ambident reagents but the reaction of Li[CH 2 C( O)Ph] with Ph 2 PCl in THF affords the ketophosphine Ph 2 PCH 2 C(O)Ph in a completely chemoselective manner. The same holds true with Li[CH 2 C( O)NPh 2 ] which leads to Ph 2 PCH 2 C(O)NPh 2 ( L 1 ). , Related 2-(diphenylphosphino)acetamide ligands have been prepared by reaction of KPPh 2 with ClCH 2 C(O)NHR (R = H, Me, Ph) . The reactivity of stable metal complexes containing P-coordinated α-phosphino enolates [Ph 2 PCH C( O)R] - (R = OEt, Ph) toward electrophiles has accordingly given rise to reactions which led to C enolate −electrophile or O enolate −electrophile bond formation.…”

“…They were characterized by their different chemical shifts in 1 H, 31 P{ 1 H} and 13 C{ 1 H} NMR spectroscopies (Table 1). 23 The reactivity of stable metal complexes containing P-coordinated…”

Bonding and Organic and Inorganic Reactivity of Metal-Coordinated Phosphinoenolates and Related Functional Phosphine-Derived Anions

“…In our case, the function Z will represent an ester, a carboxylate, a ketone, an amide, − a nitrile group, or an oxazoline moiety , situated in the β-position to the phosphorus atom as in ligands L 1 to L 7 , respectively. The synthetic principle that first led to L 2 and L 3 , namely the reaction of the corresponding lithium enolate Li[CH 2 C(O)R] with a chlorophosphine, , has found numerous applications.…”

“…11 At variance with these functional phosphines, R-stabilized phosphoylides of the type R 3 Pd CHsZ do not interact with metals via the P atom and will not be considered here; their behavior has been discussed elsewhere. 12,13 In our case, the function Z will represent an ester, 14 a carboxylate, 15 a ketone, 16 an amide, [17][18][19] a nitrile group, 14 or an oxazoline moiety 20,21 situated in the β-position to the phosphorus atom as in ligands L 1 to L 7 , respectively. The synthetic principle that first led to L 2 and L 3 , namely the reaction of the corresponding lithium enolate Li[CH 2 C(O)R] with a chlorophosphine, 16,22 has found numerous applications.…”

Platinum group metal functionalized phosphine complexes. Part 2. Phosphinoamide rhodium(I), iridium(I), palladium(II) and platinum(II) complexes

“…The complexes obtained were brown (1), pale yellow (2) and yellow (3). (4); Me, (5); Ph, (6)]. A N 2 purged CH2C12 solution of RhC1-(CO)(PPh3) 2 (0.20 g, 0.29 mM) was treated with an equimolar quantity of HDPA (0.070g), MDPA (0.075 g) or PDPA (0.093 g) under reflux for 3-4 h. Concentration of the reaction mixture and addition of n-C6Ha2 yielded yellow products.…”