Crystal Structure of {(PPh_3)_2RuB_(10)H_8[(CH_3)_2CHO]_2}

The title compound (Ⅰ) has been synthesized by the reaction of [RuCl2(PPh3)3], closo-[B10H10]2- and PhCH(OH)COOH in (CH3)2CHOH solution. The re-action gave two main products Ⅰ and Ⅱ. Crystals of the title compound (Ⅰ) suitable fora single crystal X-ray diffraction analysis were recrystailized from n-pentane/CH2Cl2 so-lution. Its structure was determined by X-ray crystallography analysis. The crystal of{(PPh3)2RuB10 H8 [(CH3)2CHO]2} (Ⅰ) is monoclinic, space group P21/n, Mr =860. 01, with a= 12. 927(2), b= 23. 672(6), c= 14. 090(4) A, β=93. 22(2)°, V=4305 A3, Dc= 1. 327 g/cm3, Z= 4, λ(MoKα) =0. 71073A, μ=4. 6 cm-1, F(000) =1776, R = 0. 059, Rw = 0. 075, S = 2. 62. The cluster structure is based on a closoeleven-vertex {RuB10 } polyhedron skeleton with two replacing isopropoxy and twoPPh3 groups.

Synthesis and Crystal Structure of{(PPh_3)_2CIRuCIRu(PPh_3) B_(10)H_8[OCH(CH_3)_2)]_2}

The title compound has been synthesized by the reaction of [RuCl2-(PPh3)3], closo-[B10H10]2- and PhCH(OH)COOH in (CH3)2CHOH solution. Crystalsof the title compound suitable for a single crystal X-ray diffraction analysis were recrystallized from n-pentane/CH2Cl2 solution. The crystal is monoclinic, space group P21,/n,Mr=1294. 19, with a=11. 591 (6), b=23. 993(4), c=24. 900(4) A, β=90. 52(2), V= 6925(4) A3, Dc= 1.241 g/cm3, Z=4, A(MoKa) =0. 71073 A, P=6. 2cm-1, F(000)=2640, R=0. 046, wR2=0. 083, S=1. 09. The cluster is a bimetallicspecies in which the second ruthenium center is bound exopolyhedrally to the compound{(PPh3)2RuB10H8[OCH (CH3)2]2 } via an Ru (1) -C;(1)-Ru (2) bridge and Ru (2) B(6) and Ru(2)-B(7) bonds.

Synthesis and Crystal Structure of ｛( P Ph_3)_2 Cl Ru( μ- Cl) Ru( P Ph_3) B_(10)H_7〔 O C H( C H_3)_2〕_3｝·0 .4( H_2O)

The title compound has been synthesized by the reaction of 〔RuCl 2(PPh 3) 3〕 and closo 〔B 10 H 10 〕 2- in (CH 3) 2CHOH solution. Crystals suitable for a single crystal X ray diffraction analysis were obtained from n pentane diffused to CH 2Cl 2 solution. The crystal {(PPh 3) 2ClRu( μ Cl)Ru(PPh 3)B 10 H 7〔OCH(CH 3) 2〕 3}·0.4(H 2O) is monoclinic , space group P2 1/n , M r= 1359.47, with a=19.434(4), b =14.340(4), c=25.865(9) , β= 95.48(3)°, V=7175(4) 3, D c =1.258 g/cm 3, Z=4, λ (Mo Kα )=0.71073, μ=6.03 cm -1 , F(000)=2784, R=0.0631, wR 2 = 0.1425, S =1.001. The title compound is a bimetallic species in which the second ruthenium center is bound to the cluster {(PPh 3)RuB 10 H 7〔OCH(CH 3) 2〕 3} via an Ru-Cl-Ru and two Ru-H-B-Ru bridges. The third isoproxy group replaces a hydrogen atom on B(10) of the cage, which indicates the activity of the cage.

Synthesis and Crystal Structure of〔( PPh_3)( CH_3 COS) _2 NiB_(10) H_(10)〕·0 .4( C_5 H_(12))

The title compound 〔(PPh 3)(CH 3COS) 2NiB 10 H 10 〕·0.4(C 5H 12 ) has been synthesized by the reaction of 〔NiCl 2(PPh 3) 2〕, closo 〔B 10 H 10 〕 2- and CH 3COSH in CH 2Cl 2 solution. It was recrystallized from n pentane/CH 2Cl 2 solution and its structure was determined by X ray diffraction analysis. The crystal is triclinic, space group P1, M r= 618.23, with a=10.049(1), b=12.638(2), c=14.077(2) , α=110.13(1), β=87.65(1), γ=96.01(1)°, V=1669.3(4) 3, D c =1.230 g/cm 3, Z=2, λ (Mo Kα )=0.71073 , μ =7.76 cm -1 , F (000)=642. The final refinement is converged with R =0.042 (5986 observed reflections with I≥2σ(I)), wR 2 =0.151. The cluster is a nido eleven vertex {NiB 10 } cage with the Ni atom in the open NiB 4 face. Cyclizations resulting in two five membered rings, Ni(7)-S(1)-C(1)-O(1)-B(2) and Ni(7)-S(2)-C(2)-O(2)-B(3), have occurred.

簇外羧环化的十一顶钌、铂和镍十硼烷簇合物的结构研究

簇外羧环化的十一顶钌、铂和镍十硼烷簇合物结构表明：６种钌簇合物均为闭式结构，按１２４２２（原子比）的方式堆积，可形成１个或２个簇外五员环；２种铂簇合物与５种镍簇合物均属巢式结构，铂簇合物形成１个簇外五员环，镍簇合物则可形成２个甚至３个簇外五员环．在镍簇合物中，参与环化的Ｎｉ—Ｂ距离比相应的未参与环化的距离明显缩短。