The 16-electron dithiolene complexes (p-cymene)M[S2C2(B10H10)] (M = Ru, Os) containing both η6(p-cymene) and η2-(ortho-carborane-dithiolate):: adduct formation with Lewis bases, and X-ray crystal structures of (p-cymene)-Ru[S2C2(B10H10)](L) (L = PPh3) and {(p-cymene)-Ru[S2C2(B10H10)]}2(μ-LL) (LL = Ph2PCH2CH2PPh2 and N2H4)
The 16-electron dithiolene complexes (p-cymene)M[S2C2(B10H10)] (M = Ru, Os) containing both η6(p-cymene) and η2-(ortho-carborane-dithiolate):: adduct formation with Lewis bases, and X-ray crystal structures of (p-cymene)-Ru[S2C2(B10H10)](L) (L = PPh3) and {(p-cymene)-Ru[S2C2(B10H10)]}2(μ-LL) (LL = Ph2PCH2CH2PPh2 and N2H4)
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DOI：
10.1016/s0022-328x(99)00692-0
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发表时间：
2000-03-25
影响因子：
2.3
通讯作者：
Milius, W
中科院分区：
文献类型：
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作者：
Herberhold, M;Yan, H;Milius, W
η（6）-芳烃配合物[（p-cymene）MCl_2]（2）（M = Ru，Os; p-cymene = 4-异丙基甲苯）与1，2-二碳环十二硼烷-1，2-二硫醇二锂（a）反应，得到新的16位二硫杂环戊烯配合物（p-cymene）M[S_2C_2（B_（10）H_（10）]（M = Ru（1），Os（1A））。将单齿刘易斯碱（L）加成到1上，得到18 e二硫代酚盐络合物，（对伞花烃）Ru[S2 C2（B10 H10）]（L）（L = PPh3（2），P（OMe）（3）（3），NH3（4），NC5H5（5），CO（6），（CNBu）-Bu-t（7），SEt2（8），SC4H8（9），CN-（10）和SCN-（11）），而双齿桥连刘易斯碱（LL）得到中心对称的双核类似物{（对伞花烃）Ru[S_2C_2（B_（10）H_（10））]}（2）（LL）（LL = Ph_2PCH_2CH_2PPh_2（12），N_2H_4（13）和4，4 ′-联吡啶（14））。刘易斯碱加合物的稳定性取决于配位原子的性质，其稳定性顺序为C > P > N > S > O。通过它们的H-1-、C-13-和B-11-NMR谱表征加合物，并测定2、12和13的X-射线晶体结构。2和12中的膦配体使1中的平面二硫杂环RuS 2 C2沿着S. S矢量（2中为25.6度，12中为21.0度）比13中的肼配体（7.5度）。(C)2000 Elsevier Science S.A. All rights reserved.
The reaction of the eta(6)-arene complexes [(p-cymene)MCl2](2) (M = Ru, Os; p-cymene = 4-isopropyl-toluene) with dilithium 1,2-dicarba-closo-dodecaborane-1,2-dithiolate (a) leads to the new 16e dithiolene complexes (p-cymene)M[S2C2(B10H10)] (M = Ru (1), Os (1A)). Addition of monodentate Lewis bases (L) to 1 gives 18e dithiolate complexes of the type (p-cymene)Ru[S2C2(B10H10)](L) (L = PPh3 (2), P(OMe)(3) (3), NH3 (4), NC5H5 (5), CO (6), (CNBu)-Bu-t (7), SEt2 (8), SC4H8 (9), CN- (10) and SCN- (11)), whereas bidentate bridging Lewis bases (LL) give centrosymmetric binuclear analogues, {(p-cymene)Ru[S2C2(B10H10)]}(2)(LL) (LL = Ph2PCH2CH2PPh2 (12), N2H4 (13) and 4,4'-dipyridine (14)). The stability of the Lewis base adducts depends on the nature of the ligating atom and decreases in the order C > P > N > S > O. The adducts were characterized by their H-1-, C-13- and B-11-NMR spectra, and X-ray crystal structures were determined for 2, 12 and 13. The phosphane ligands in 2 and 12 cause stronger folding of the planar dithiolene ring RuS2C2 in 1 along the S ... S vector (by 25.6 degrees in 2 and 21.0 degrees in 12) than the hydrazine ligand in 13 (7.5 degrees). (C) 2000 Elsevier Science S.A. All rights reserved.