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Natalia V. Belina Vyacheslav V. Sushev Georgy K. Fukin Eugene V. Baranov Gleb A. Abakumov 《Journal of organometallic chemistry》2010,695(4):637-3522
The reaction of bromophosphite (ArO)2PBr {(ArO)2P = CH2(6-tBu-4-Me-C6H2O)2P} with lithium salt of 1,2-diphenylhydrazine gave phosphitohydrazine (ArO)2P-NPh-NPhH (2) in 64% yield. The last one reacted with Co[N(SiMe3)2]2 to afford cobalt(II) iminophosphoranate (PhNP(OAr)2-NPh-)2Co (3), which is the result of isomerisation of the phosphitohydrazide ligand in coordination sphere of divalent cobalt. 相似文献
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Vyacheslav V. Sushev Yuriy A. Min’ko Natalia V. Belina Yuriy A. Kurskiy Olga V. Kuznetsova Georgy K. Fukin Evgenii V. Baranov Vladimir K. Cherkasov Gleb A. Abakumov 《Journal of organometallic chemistry》2006,691(5):879-889
The reaction of diphosphinohydrazine PhNH-N(PPh2)2 (1) with cobalt(II) silylamide, Co[N(SiMe3)2]2, proceeds via formation of unstable phosphinohydrazide complex Co[NPh-N(PPh2)2]2 followed by rearrangement to a new chelating compound Co(NPh-PPh2N-PPh2)2 (2). Disproportionation of nickel(I) silylamide, (Ph3P)2Ni-N(SiMe3)2, in the presence of 1, yields Ni(0) and Ni(II) phosphinoamide complexes: Ni[(Ph2P)2N-NPhH]2 (3), Ni(NPh-PPh2N-PPh2)2 (4). X-ray analysis reveals tetrahedral environment of the cobalt atom in 2 and square-planar environment of the nickel atom in cis-4. In contrast to the crystalline patterns, the solutions of 2 in THF or toluene have EPR signal which is typical to square-planar low-spin d7 cobalt complex. The reactions of 2 with dioxygen, elemental sulfur and diphenyldiazomethane led to the spirocyclic insertion products Co(NPh-PPh2N-PPh2X)2 (X = O, S, NNCPh2) while the absorption of carbon monoxide is reversible. 相似文献
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Yana V. Fedotova Vyacheslav V. Sushev Tatiana G. Mushtina Georgy K. Fukin Lev N. Zakharov 《Journal of organometallic chemistry》2004,689(19):3060-3074
The reactions of phosphinohydrazines ArNH-N(Ar)-PPh2 {Ar = Ph (2a), p-But-C6H4- (2b)} with metal silylamides M[N(SiMe3)2]n, {M = Fe(II), Fe(III), Co(II), Ni(I), Cu(I)} or the reactions of lithium salts ArN(Li)-N(Ar)-PPh2 with metal halides (GeCl2, ZnCl2, FeBr2, CoCl2, NiBr2, CrCl3, MnCl2) are strongly dependent on nature of a metal and its ligand environment.Early transition metals or non-transition metals form stable phosphinohydrazides M[N(Ar)N(Ar)PPh2]n {M = Li, Zn, Ge(II), Mn(II), Cr(III), Fe(II)}.Starting ligand 2a and germylene Ge(NPhNPhPPh2)2 (7) were characterized by X-ray analysis.Germanium is coordinated additionally with a phosphorus atom of one of the diphenylphosphine groups.The distance Ge?P was found to be 2.563(1) Å.This coordination leads to an appreciable increase in a pyramidal geometry of nitrogen atoms relatively to a non-coordinated fragment.Late transition metals (Co, Ni, Cu) and metals with enhanced oxidation state (Fe3+) cause transformation of a phosphinohydrazide ligand.For Co(II), Ni(II), Fe(III) this leads quantitatively to aminoiminophosphoranates M(NAr-PPh2NAr)n.Complex Co[N(C6H4But)-PPh2N-C6H4But]2 (11) was characterized by X-ray analysis.Nickel(I) silylamide, (Ph3P)2NiN(SiMe3)2, being reacted with 2a yields azobenzene complex, (Ph3P)2Ni(PhNNPh), while copper(I) silylamide originally forms (PhNH-NPh-PPh2)2CuN(SiMe3)2 (18).Heating of the latter in toluene solution yields insoluble copper(I) diphenylphosphide, azobenzene, 2a and hexamethyldisilazane.The reaction of hydrazobenzene with Ph2PCl (1:1) in methylene chloride for three days gives aminoiminophosphorane dihydrochloride[PhNH-PPh2NPh] · 2HCl (3) in quantitative yield. 相似文献
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Vyacheslav V. Sushev Yurii A. Kurskii Georgy K. Fukin Gleb A. Abakumov 《Journal of organometallic chemistry》2005,690(7):1814-1821
The reactions of NiII[(PPh2)2N]2 (2) with various reagents are described. Addition of two moles of carbon monoxide to 2, at 20 °C and atmospheric pressure leads to the redox coupling of dppa ligands and formation of zero-valent nickel complex (CO)2Ni(Ph2PNPPh2PPh2NPPh2) (4). The nickel atom in 4 has a tetrahedral coordination and is incorporated into the NiP4N2 ring adopting a distorted chair conformation with phosphorus-phosphorus bond length 2.2777(5) Å. Contrary to CO, sulphur dioxide reacts with 2 to form simple adduct (SO2)NiII[(PPh2)2N]2. The reaction of 2 with allyl bromide runs as alkylation of dppa ligand to form All-N(PPh2)2NiBr2. The reduction of 2 with metallic sodium in THF gives Ni(0) complex, HN(PPh2)2Ni(Ph3P)2 (7). The electrochemical reduction of 2 in CH2Cl2 takes place in two steps: reversible one-electron and quasi-reversible three-electron step. 相似文献
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