32109-09-4Relevant articles and documents
Electron-transfer Reactions in Nitrogen Fixation. Part 1. The Electrosynthesis of Dinitrogen, Hydride, Isocyanide, and Carbonyl Complexes of Molybdenum: Intermediates, Mechanisms, and Energetics
Al-Salih, Talib I.,Pickett, Christopher J.
, p. 1255 - 1264 (1985)
Dinitrogen, hydride, carbonyl, and isocyanide complexes of Mo0 and W0 can be electrosynthesised from the molecular substrates N2, H2, etc. and precursors trans- (M=Mo; X=Cl, Br, I, SPh, or SBun; M=W;
Reactions of molybdenum tetrahydrido complex with halohydrosilanes
Kuramochi, Satoru,Kido, Yo-Hei,Shioda, Syunsuke,Minato, Makoto,Kakeya, Masaki,Osakada, Kohtaro
, p. 165 - 169 (2010/05/15)
The thermal reactions of [MoH4(dppe)2](1, dppe = Ph2PCH2CH2PPh2)with RSiH 2Xafford [MoH2X(dppe)-{[Ph2PCH 2CH2P(Ph)C6H4-o]RXSi-P,P,Si}](R = Ph, X = Cl (5a); R = cycfo-C6H11, X = Cl (5b); and R = Ph, X = Br (6)) by activation of the Si-H bond of the silanes and the ortho C-H bond of the phenyl group in the dppe ligand. Reduction of the Si-Cl and Mo-Cl bonds in 5a with LiAlH4 leads to the formation of the original complex 1 as a result of unusual Si-C bond cleavage. Meanwhile, dehalogenative reduction of 5a using zinc metal gives the known compound [MoH 3{[Ph2PCH2CH2P(Ph)C 6H4-o]2(Ph)Si-P,P,P,P,Si}](2). The experimental results reported herein provide certain evidence for the involvement of the silylene species in the unusualformation of the present polydentate phosphinoalkyl-silylligands.
Synthesis and reactivities of pyrrolylimido complexes of molybdenum and tungsten: Formation of pyrrole and N-aminopyrrole from molecular nitrogen
Seino, Hidetake,Ishii, Youichi,Sasagawa, Takao,Hidai, Masanobu
, p. 12181 - 12193 (2007/10/03)
Hydrazido(2-) complexes trans-[MX(NNH2)(dppe)2]+ (M = Mo, W; X = F, Cl; dppe = Ph2PCH2CH2-PPh2) and cis,mer-[WX2(NNH2)(PMe2Ph)3] (X = Cl, Br), which are readily derived from trans-[M(N2)2(dppe)2] (1) and cis-[W(N2)2(PMe2Ph)4] by protonation, condensed with 2,5-dimethoxytetrahydrofuran to afford pyrrolylimido complexes of the type trans-[MX(NNCH=CHCH=CH)(dppe)2]+ (3+) and cis,mer-[WX2(NNCH=CHCH=CH)(PMe2-Ph)3] (6), respectively. Their structures were characterized spectroscopically and further confirmed by X-ray diffraction study. Electrophilic substitution reactions at the pyrrole ring in complexes 3+ occurred selectively at the β-position to give the corresponding β-substituted pyrrolylimido complexes trans-[MX(NNCH=C(E)CH=CH)(dppe)2]+ (E = Br, CN, SO3-, COR), although only chlorination of 3+ with N-chlorosuccinimide in THF took place predominantly at the α-position. This β-regioselectivity is in sharp contrast to the α-regioselectivity of free pyrrole and is probably caused by the steric effect of the dppe ligands. Complexes 3+ were readily reduced under ambient conditions with LiAlH4 to liberate pyrrole and N-aminopyrrole in high yields. Further, the tetrahydrido complexes [MH4(dppe)2], which can be converted back into the original dinitrogen complexes 1, were recovered in moderate yields after the reduction. This accomplishes the synthetic cycle for pyrrole and N-aminopyrrole starting from the dinitrogen complexes 1. β-Heptylpyrrole was also prepared by starting from 3c+ (M = W, X = Cl) by the β-selective heptanoylation followed by the reduction with LiAlFL;. On the other hand, reduction of 6b (X = Br) with LiAlH4 predominantly produced pyrrole, whereas treatment of 6b with KOH/EtOH liberated N-aminopyrrole in a high yield.
Bisdihydrogenhydridoiron(II) Tetraphenylborate as a Model for the Function of Nitrogenases
Hills, Adrian,Hughes, David L.,Jimenez-Tenorio, Manuel,Leigh, G. Jeffery,Rowley, Adrian T.
, p. 3041 - 3050 (2007/10/02)
The trihydride complex (+) (dmpe = Me2PCH2CH2PMe2) is best represented as (+), with the H-H separation in the H2 being ca. 0.81 Angstroem.The H2 can be replaced by N2, CO, MeCN, MeNC and C2H4.The dinitrogen complex (+) may be deprotonated to yield the solution-stable, trigonal-bipyramidal species , which can be reprotonated by HCl to yield , N2, H2 and NH3.The crystal structures of BPh4 and BPh4 have been determined.
