spectra of [L(2)MCl(2)] [M = Pd, 9; M = Pt, 10] and of the organometallic derived compounds [L(2)Pd(PPh(3))], 11, and [L(2)Pd(Cl)(eta(2)-CH(2)Ph)], 12, consist of a pair of doublets, with the H(endo)() coupled to the P of the metallacycle. The CH(2)-metal close proximity drives the electrophilic metalation of the bridging methylene by RhCl(3) to form [L(2)Rh(Cl)(2)(MeCN)], 13, [L(2) = Ph(2)P(o-C(6)H(
新型二膦参考配体L(2),6,Ph(2)P(oC(6)H(4)CH(2)C(6)H(4)-o)PPh(2)的多步合成已精简,可以在ca上进行制备。20克秤。它与各种金属碎片形成金属环。所得的非常坚硬的船形构象迫使桥接亚甲基的质子(H(endo)())紧靠金属,从而使这些质子(H(endo)(),H(exo )())非对映体。[L(2)MCl(2)]的NMR光谱[M = Pd,9; M = Pt,10]和有机金属衍生化合物[L(2)Pd(PPh(3))],11和[L(2)Pd(Cl)(eta(2)-CH(2)Ph) ],12,由一对双键组成,其中H(endo)()与金属环的P相连。CH(2)-金属紧密接近通过RhCl(3)驱动桥连亚甲基的亲电金属化形成[L(2)Rh(Cl)(2)(MeCN)],13 [L(2)= Ph(2)P(oC(6)H(4)CHC(6)H(4)-o)PPh(2)]。一个
Alkylidyne[pyrazol-1-yl)borato]tungsten complexes:metal–carbon triple bonds as four-electron donors
作者:Michael Green、Judith A. K. Howard、Alun P. James、Alasdair N. de M. Jelfs、Christine M. Nunn、F. Gordon A. Stone
DOI:10.1039/c39840001623
日期:——
The tungstenComplexes [W(CR)(CO)2(R′Bpz3)](R = Me or C6H4Me-4,R′H; R = C6H4Me-4,R = pz = pyrazol-1-yl) have been prepared and used to synthesise heteronuclear di-and tri-metal compounds with bridging alkylidyne ligands;the structures of the species [WCC6H4Me-4)(CO)2(Bpz4)] and [FeW(µ-CC6H4Me-4)(CO)5(HBpz3)] have been established by X-ray diffraction.
钨配合物[W(CR)(CO)2(R'Bpz 3)](R = Me或C 6 H 4 Me-4,R'H ; R = C 6 H 4 Me-4,R = pz =吡唑-1-基)已制备并用于合成具有桥接亚烷基配体的杂核二金属和三金属化合物;该化合物的结构[W CC 6 H 4 Me-4)(CO)2(Bpz 4)]和[FEW(μ-CC 6 H ^ 4 ME-4)(CO)5(HBpz 3)]已通过建立的X射线衍射。
Chemistry of polynuclear metal complexes with bridging carbene or carbyne ligands. Part 56. Synthesis of iron–molybdenum compounds; crystal structures of [FeMo(µ-CR)(CO)<sub>6</sub>(η-C<sub>5</sub>H<sub>5</sub>)] and [FeMo<sub>2</sub>(µ<sub>3</sub>-RC<sub>2</sub>R)(CO)<sub>6</sub>(η-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>](R = C<sub>6</sub>H<sub>4</sub>Me-4)
作者:M. Esther Garcia、John C. Jeffery、Paul Sherwood、F. Gordon A. Stone
DOI:10.1039/dt9870001209
日期:——
C6H4Me-4) react in Et2O at room temperature to give the dimetal complex [FeMo(µ-CR)(CO)6(η-C5H5)], the structure of which has been established by X-ray diffraction. Four CO groups are terminally bound to the iron atom and two to the molybdenum, with the latter also carrying the η-C5H5 ligand. The dimensions of the dimetallacyclopropene ring are Fe–Mo 2.823(1), µ-C–Fe 2.008(5), and µ-C–Mo 1.921(5)Å. Excess
等量的[Fe 2(CO)9 ]和[沫(CR)(CO)2(η-C 5 H ^ 5)](R = C 6 H ^ 4 ME-4)的Et反应2 ö在室温下得到双金属配合物[钼铁(μ-CR)(CO)6(η-C 5 H ^ 5)],其结构已被建立的X射线衍射。四个CO基团末端结合到铁原子和两个与钼,后者还携带η-C 5 H ^ 5配体。双金属环丙烯环的尺寸为Fe–Mo 2.823(1),µ-C–Fe 2.008(5)和µ-C–Mo 1.921(5)Å。过量的[Fe的2(CO)9 ]和[沫(CR)(CO)2(η-C 5 H ^ 5)]在室温下在Et反应2 O操作得到三金属化合物的[Fe 2沫(μ 3 - CR)(μ-CO)(CO)8(η-C 5 H ^ 5)]。相反,一当量的壬羰基二铁与两当量的甲苯基甲基二炔钼化合物之间的反应产生了46价电子的铁二钼簇[FeMo 2(µ 3 -RC 2 R)(CO)6(η-C
Ring Opening of (Spiro[2.4]hepta-4,6-diene)tricarbonyliron: A Revisit
作者:Yuan-Te Fu、Pei-Chi Chao、Ling-Kang Liu
DOI:10.1021/om970703y
日期:1998.1.1
(Spiro[2.4]hepta-4,6-diene)tricarbonyliron (2) self-converts to the tethered acyl complex (CO)2FeC(O)CH2CH2(η5-C5H4) (3) when refluxed for 1 h in common organic solvents. The reaction of 2 with an external electrophile (CPh3+, H+) opens the three-membered ring, resulting in the cation (η5-C5H4CH2CH2R)Fe(CO)3+ whose structure was determined by spectroscopic methods and confirmed by X-ray analysis of
Cooperative effects in π-ligand bridged dinuclear complexes XXII. New dinuclear bis(cyclopentadienediyl)ketone complexes containing molybdenum, tungsten, cobalt and iron
5(Co)–C5Me4)]Co(CO)2 (4a) along with the homodinuclear complex (CO)2Co[(η5-C5H4)C(O)(η5-C5Me4)]Co(CO)2 (5), the comparable reaction of 3b with Co2(CO)8 results in the formation of the heterodinuclear complex Me(CO)3W[(η5(W)–C5H4)C(O)(η5(Co)–C5Me4)]Co(CO)2 (4b) only. The metal–metal bound complexes [(η5(M)–C5H4)C(O)(η5(M′)–C5Me4)]MM′(CO)6 (M–M′) (M=W, M′=Mo: 8; M=M′=W: 9; M=M′=Mo: 10) are synthesized