Aminocarbyne coupling reactions at M(Ph2PCH2CH2PPh2)2(M = Mo or W) sites. Synthesis and properties of the diaminoacetylene complexes trans-[MX(η2-MeHNCCNHMe)-(Ph2PCH2CH2PPh2)2]A (X = F, Cl or ClO4; A = BF4′PF6′HCl2or ClO4) and of their di(aminocarbyne)-type precursors
作者： Yu Wang , João J. R. Fraústo Da Silva , Armando J. L. Pombeiro , Maria Angela Pellinghelli , António Tiripicchio
DOI: 10.1039/DT9950001183
关键词:
摘要: Treatment of trans-[M(CNMe)2(dppe)2]1(M = Mo or W, dppe Ph2PCH2CH2PPh2) in CH2Cl2 with HA (A BF4′ PF6′ Cl ClO4) gives the diaminoacetylene complexes trans-[MX(η2-MeHNCCNHMe)(dppe)2]A 2(X F, ClO4; A HCl2 ClO4). The crystal structure trans-[MoF(η2-MeHNCCNHMe)(dppe)2][BF4] has been determined. key intermediate reaction, trans-[M(CNHMe)2(dppe)2]A23(A ClO4), also isolated and shown to be best viewed as a ‘iminomethylenium’ species CNHMe. acetylenic CC triple bond 2 undergoes base-induced cleavage (e.g., by LiBun) form parent complex 1.
rsc.org
sci-hub.se 参考文章(38)
A. Mayr, The Role of Nucleophiles and Electrophiles in Coupling Reactions of Alkylidyne Ligands Transition Metal Carbyne Complexes. pp. 219- 230 ,(1993) , 10.1007/978-94-011-1666-4_25
James A. Ibers, Lonsdale, Kathleen, Dame, John S. Kasper, Gerard D. Rieck, Walter C. Hamilton, Norman Fordyce McKerron Henry, Caroline H. MacGillavry, International tables for X-ray crystallography UT Back-in-Print Service. ,(1962)
Andreas Mayr, Hans Hoffmeister, Recent Advances in the Chemistry of Metal-Carbon Triple Bonds Advances in Organometallic Chemistry. ,vol. 32, pp. 227- 324 ,(1991) , 10.1016/S0065-3055(08)60481-5
João J.R.Fraústo da Silva, Maria Angela Pellinghelli, Armando J.L. Pombeiro, Raymond L. Richards, António Tiripicchio, Yu Wang, Aminocarbyne coupling reactions leading to the bis(amino)acetylene complexes trans-[MF(η2-MeHNCCNHMe)-(Ph2PCH2CH2PPh2 Journal of Organometallic Chemistry. ,vol. 454, ,(1993) , 10.1016/0022-328X(93)83255-T
Edmund M. Carnahan, Stephen J. Lippard, Reductive coupling of carbon monoxide with methyl isocyanide in a seven-coordinate niobium complex Journal of the American Chemical Society. ,vol. 112, pp. 3230- 3231 ,(1990) , 10.1021/JA00164A064
Armando J. L. Pombeiro, Raymond L. Richards, Reactivity of carbyne and carbene complexes of molybdenum and tungsten Transition Metal Chemistry. ,vol. 5, pp. 55- 59 ,(1980) , 10.1007/BF01396869
Joseph L. Templeton, Bennett C. Ward, Carbon-13 chemical shifts of alkyne ligands as variable electron donors in monomeric molybdenum and tungsten complexes Journal of the American Chemical Society. ,vol. 102, pp. 3288- 3290 ,(1980) , 10.1021/JA00529A086
Joseph Chatt, Armando J. L. Pombeiro, Raymond L. Richards, Hydrido-complexes of molybdenum and tungsten with isonitrile and carbyne-type ligands Journal of the Chemical Society, Dalton Transactions. pp. 1585- 1590 ,(1979) , 10.1039/DT9790001585
Edmund M. Carnahan, Stephen J. Lippard, Mechanistic studies of the reductive coupling of isocyanides in seven-co-ordinate molybdenum complexes; X-ray crystal structures of [Mo(CNBut)6] and [Mo{CN(But)(SiMe2But)}(CNBut)5][O3SCF3] Journal of The Chemical Society-dalton Transactions. pp. 699- 706 ,(1991) , 10.1039/DT9910000699
A.C. Filippou, Proton-induced coupling of a tertbutylisocyanide with a diethylaminocarbyne to yield an alkyne ligand at a single tungsten centre Polyhedron. ,vol. 9, pp. 727- 738 ,(1990) , 10.1016/S0277-5387(00)80282-X