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• 86632-52-2 LiCH(CN)(P(C₆H₅)2) 
• 31201-88-4 diphenylphosphanyl-acetonitrile 

Relevant academic research and scientific papers

Complexes of functional phosphines. 6. Five-membered palladium or platinum metallocycles resulting from nucleophilic attack of α-phosphino carbanions on organonitriles. Synthesis and crystal structure of trans-Pt[Ph2PC(COOC2H5)C(Ph)NH]2 and Pd(C N)Cl[μ-Ph2PCH2C(NH)C(CN)PPh2]Pd(C N) [C N = o-C ...

Full title: Complexes of functional phosphines. 6. Five-membered palladium or platinum metallocycles resulting from nucleophilic attack of α-phosphino carbanions on organonitriles. Synthesis and crystal structure of trans-Pt[Ph2PC(COOC2H5)C(Ph)NH]2 and Pd(C N)Cl[μ-Ph2PCH2C(NH)C(CN)PPh2]Pd(C N) [C N = o-C6H4CH2N(CH3)2]. Reaction of 2 equiv of Li(Ph2PCHY) (Y = CN, COOEt) with PtCl2(PhCN)2 proceeds via nucleophilic attack on the coordinated nitriles afforded trans-Pt[Ph2PC(Y)C(Ph)NH]2 (Y = CN, 1; Y = COOEt, 2). The crystal and molecular structure of 2 has been determined by X-ray diffraction methods. The compound crystallizes in the space group P21/c of the monoclinic system with two formula units in a cell of dimensions a = 10.064 (3) A?, b = 23.272 (3) A?, c = 8.964 (1) A?, and β = 77.28 (1)°. The structure has been refined by least-squares methods to a final value of the conventional R factor of 0.047 on the basis of 3163 independent intensities. The molecule is centrosymmetric. The coordination about platinum is square planar, and there are only small deviations from planarity in the two metallocycles. The Pt-P bonds (2.280 (3) A?) and the Pt-N bonds (1.992 (8) A?) fall in a normal range; the shortness of the C(Ph)N bonds (1.32 (1) A?) suggests electron delocalization within the P N chelate. An isoelectronic unsaturated metallocycle was found in Pd(C N)Cl[μ-Ph2PCH2C(NH)C(CN)PPh2]Pd(C N) (5; C N = o-C6H4CH2N(CH3)2), the formation of which is interpreted as resulting from nucleophilic attack of the uncoordinated nitrile in the complex (C N)Pd(Cl)Ph2PCH2CN by "(C N)Pd(Ph2PCHCN)" (6), itself generated by reaction of [(C 7 N)Pd(μ-Cl)]2 with 2 equiv of Li(Ph2PCHCN). The structure of complex 5·2CH2Cl2 was determined by single-crystal X-ray diffraction methods and refined to conventional R = 0.024. The compound crystallizes in the monoclinic crystal system of space group PZ1 with a = 10.234 (7) A?, b = 23.743 (10) A?, c = 10.663 (7) A?, β = 107.06 (2)°, and Z = 2. The molecule consists of two (C N)Pd cyclopalladated moieties linked by the bridging six-electron donor multifunctional anionic ligand μ-[Ph2P(1)CH2C(NH-)CH(CN)P(2)Ph 2]. This original ligand is P(1) bonded to Pd(1) [Pd(1)-P(1) = 2.255 (2) A?] and (P(2),N) bonded in a chelate manner to Pd(2) [Pd(2)-P(2) = 2.239 (2), Pd(2)-N(3) = 2.092 (6) A?]. The coordination about Pd(1) is completed by a Cl ligand [Pd(1)-Cl = 2.405 (2) A?], trans with respect to P(1). The P(2)N unsaturated chelating moiety about Pd(2) is characterized by a short C(2)N(3) bond (1.30 (1) A?) resembling the situation found in 2. The electron delocalization in 2 and 5 is related to the structural and spectroscopic data of the molecules. Spectroscopic (IR and 1H, 13C, and 31P{1H} NMR) data in solution are consistent with the solid-state structure of the new compounds.