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The reactivity of [MoS(4)](2-) (1) toward PMe(3) was explored in the presence and absence of proton donors. Whereas MeCN solutions of (Et(4)N)(2)[MoS(4)] and PMe(3) are stable, in the presence of H(2)S such solutions catalyze formation of H(2) and SPMe(3). Addition of NH(4+) to such solutions afforded MoS(2)(PMe(3))(4) (2), which can be prepared directly from (NH(4))(2)[1]. Compound 2 is reactive toward thiols via a process proposed to involve the initial dissociation of one PMe(3) ligand, a hypothesis supported by the relative inertness of trans-MoS(2)(dmpe)(2). Benzene solutions of 2 react with EtSH to give Mo(2)(mu-S)(mu-SH)(PMe(3))(4)(SEt)(3) (3Et). Analogous reactions with thiocresol (MeC(6)H(4)SH) and H(2)S gave Mo(2)(mu-S)(mu-SH)(PMe(3))(4)(SR)(3) (R = tol, H). Crystallographic analyses of 3Et, 3H, and 3tol indicate dinuclear species with seven terminal ligands and a Mo(2)(mu-SR)(mu-S) core (r(Mo)(-)(Mo) = 2.748(1) A). From reaction mixtures leading to 3Et from 2, we obtained the intermediate Mo(IV)(2)(mu-S)(2)(SEt)(4)(PMe(3))(2) (4), an edge-shared bis(trigonal pyramidal) structure. Compounds 3H and 3Et react further with H(2)S to give Mo(4)(mu(2)-S)(4)(mu(3)-S)(2)(PMe(3))(6)(SH)(2) (5H) and Mo(4)(mu(2)-S)(4)(mu(3)-S)(2)(PMe(3))(6)(SEt)(2) (5Et), respectively. Analogously, W(4)(mu(2)-S)(4)(mu(3)-S)(2)(PMe(3))(6)(SH)(2) was synthesized from a methanol solution of (NH(4))(2)WS(4) with H(2)S and PMe(3). A highly accurate crystallographic analysis of (NH(4))(2)MoS(4) (R(1) = 0.0193) indicates several weak NH.S interactions. 相似文献
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van der Vlugt JI Rauchfuss TB Wilson SR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(1):90-98
The two-step one-pot oxidative decarbonylation of [Fe2(S2C2H4)(CO)4(PMe3)2] (1) with [FeCp2]PF6, followed by addition of phosphane ligands, led to a series of diferrous dithiolato carbonyls 2-6, containing three or four phosphane ligands. In situ measurements indicate efficient formation of 1(2+) as the initial intermediate of the oxidation of 1, even when a deficiency of the oxidant was employed. Subsequent addition of PR3 gave rise to [Fe2(S2C2H4)(mu-CO)(CO)3(PMe3)3]2+ (2) and [Fe2(S2C2H4)(mu-CO)(CO)2(PMe3)2(PR3)2]2+ (R = Me 3, OMe 4) as principal products. One terminal CO ligand in these complexes was readily substituted by MeCN, and [Fe2(S2C2H4)(mu-CO)(CO)2(PMe3)3(MeCN)]2+ (5) and [Fe2(S2C2H4)(mu-CO)(CO)(PMe3)4(MeCN)]2+ (6) were fully characterized. Relevant to the H(red) state of the active site of Fe-only hydrogenases, the unsymmetrical derivatives 5 and 6 feature a semibridging CO ligand trans to a labile coordination site. 相似文献
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Syntheses and Crystal Structures of New Selenido-bridged Ruthenium Clusters The reaction of Se(SiMe3)2 with [RuCl2(PPh3)3], or a mixture of [RuCl2(PPh3)3] and alkylphosphines leads to the formation of selenido-bridged ruthenium clusters. In this publication the compounds [Ru6Se8(PPh3)6] ( 1 ), [Ru6Se8(PEt3)6] ( 2 ) und[Ru6Se8(PnPr3)6] ( 3 ) are described.The compounds 1-3 contain Ru616+ cluster cores with Ru2+ and Ru3+ centers. The structures of these compounds were elucidated by single crystal X-ray structural analyses. 相似文献
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Organo-tricyanoborates as tectons: illustrative coordination polymers based on copper(I) derivatives
The first systematic study on the use of tricyanoborates as ligands is presented. The tricyanoborates [RB(CN)3]- (R = oct and Ph) can be prepared by direct cyanation of RBCl2 precursors as well as by thermolysis of the corresponding isocyanides [RB(NC)3]-. The first organo-cyanogallates [RGa(CN)3]- (R = Bu, C6H2-2,4,6-Me3) were prepared from the corresponding dichloride, the structure of Et4N[mesGa(CN3] being confirmed crystallographically. The reaction of equimolar [RB(CN)3]- (R = oct, Ph) and [Cu(MeCN)4]+ afforded two-dimensional polymers [RB(CN)3Cu(NCMe)]. The sheets arise via conjoined hexagonal B3Cu3(CN)6 rings with chair conformations. The reaction of excess [PhB(CN)3]- and [Cu(MeCN)4]+ gives the polymer [K(18-crown-6)]{Cu[PhB(CN)3]2}. Treatment of [PhB(CN)3]- with [Cu(PCy3)2(NCMe)x]PF6 gave the one-dimensional polymer [PhB(CN)3Cu(PCy3)2], wherein two of the three BCN substituents are coordinated. 相似文献
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Saeed Kamali Hongxin Wang Devrani Mitra Hideaki Ogata Wolfgang Lubitz Brian C. Manor Thomas B. Rauchfuss Deborah Byrne Violaine Bonnefoy Francis E. Jenney Michael W. W. Adams Yoshitaka Yoda Ercan Alp Jiyong Zhao Stephen P. Cramer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2013,125(2):752-756
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