1262046-46-7Relevant articles and documents
Transition metal chemistry of cyclodiphosphanes containing phosphine and amide-phosphine functionalities: Formation of a stable dipalladium(II) complex containing a Pd-P σ-bond.
Balakrishna, Maravanji S.,Venkateswaran, Ramalingam,Mague, Joel T.
experimental part, p. 11149 - 11162 (2011/01/11)
Cyclodiphosphazanes containing phosphine or phosphine plus amide functionalities {(tBuNP(OC6H4PPh 2-o)}2 (3), {tBuNP(OCH2CH 2PPh2)}2 (4), {tBuHN( tBuNP)2OC6H4PPh2-o} (5), and {tBuHN(tBuNP)2OCH2CH 2PPh2} (6) were synthesized by reacting cis-{ tBuNPCl}2 (1) and cis-[tBuHN( tBuNP)2Cl] (2) with corresponding phosphine substituted nucleophiles. The reactions of 3 and 5 with excess of elemental sulfur or selenium produce the corresponding tetra and trichalcogenides, {( tBuNP(E)(OC6H4P(E)Ph2-o)} 2 (7, E = S; 8, E = Se) and {tBuHN(tBuNP) 2OC6H4P(E)Ph2-o} (9, E = S; 10, E = Se), respectively, in quantitative yields. The reactions between 3 and [Rh(COD)Cl]2 or [M(COD)Cl]2 (M = Pd or Pt) afford bischelated complexes [Rh(CO)Cl{tBuNP(OC6H 4PPh2-o)}]2 (11), and [MCl2{ tBuNP(OC6H4PPh2-o)}]2 (12, M = Pd; 13, M = Pt) in good yield. The 1:2 reaction between 3 and [PdCl(η3-C3H5)]2 in dichloromethane resulted initially in the formation of a tripalladium complex of the type [Pd3Cl4(η3-C3H 5)2{tBuNPOC6H4PPh 2}2] (14a) which readily reacts with moisture to form an interesting binuclear complex, [Cl2Pd{μ-(PPh2C 6H4OP(μ-tBuN)2P(O)}(μ-Cl) Pd(OC6H4PPh2)] (14b). One of the palladium(ii) atoms forms a simple six-membered chelate ring, whereas the other palladium(ii) atom facilitates the moisture assisted cleavage of one of the endocyclic P-O bonds followed by the oxidation of P(iii) to P(v) thus forming a Pd-P σ-bond. The broken ortho-phosphine substituted phenoxide ion forms a five-membered palladacycle with the same palladium(ii) atom. Similar reaction of 5 with [PdCl(η3-C3H5)]2 also affords a binuclear complex [{PdCl(η3-C3H 5)}tBuNH{tBuNP}2OC6H 4PPh2{PdCl2}] (15) containing a PdCl 2 moiety which forms a six-membered chelate ring via ring-phosphorus and PPh2 moieties on one side and a PdCl(η3-C 3H5) fragment coordinating to amide bound phosphorus atom on the other side of the ring. Treatment of 3 with four equivalents of AuCl(SMe2) produces a tetranuclear complex, [(AuCl)4{ tBuNP(OC6H4PPh2)}2] (16), whereas a 1:3 reaction between 5 and AuCl(SMe2) leads to the formation of a trinuclear complex, [tBuNH{tBuNP(AuCl)} 2OC6H4P(AuCl)Ph2] (17). The crystal structures of 3, 5, 9-11 and 13-17 are reported.
