Through the reaction of Co2(CO)8 with two heterocyclic ligands of C(S)NHP(S)(C6H4OCH 3)OC(Ph)CH (L1) and C(S)NHC(CH)P(S)(Cl)N(Ph) (L 2), the two trinuclear cobalt carbonyl sulfur clusters, Co 3(CO)7(μ3-S) [μ, η2-C *N*P(S)(C6H4OCH3)OC(Ph)CH] (I) and Co3(CO)7(μ3-S) [μ, η2-S *CN*C(CH)P(S)(Cl)N(Ph)] (II), were prepared and characterized by IR, 1H NMR, 31P NMR, MS spectroscopy and X-ray crystal diffraction. The crystals of I and II are triclinic, belonging to space group P1, a = 0.84768(1) nm, b = 1.19043(3) nm, c = 1.43639(1) nm, α = 86.926(1)°, β = 81.603(3)°, γ = 88.535(2)°, V = 1.4318(5) nm3, Z = 2, Dc = 1.641g · cm-3, F(000) = 716, μ = 1.893 mm-1, R = 0.0602, Rw = 0.1515 for complex I; a = 1.2050(2) nm, b = 1.2448 (2) nm, c = 0.8951(2) nm, α = 97.49(1)°, β = 93.552(4)°, γ = 108.432(3)°, V = 1.2554(3) nm3, Z = 2, Dc = 1.841g · cm-3, F(000) = 690, μ = 2.419 mm-1, R =0.0423, Rw = 0.1075 for complex II. The structure analyses show that the Co3S frameworks of I and II are a triangular pyramid, respectively, and for which the sulfur atom as face bridging ligand and all carbonyls as terminal ligand link up with three cobalts in the cluster framework. I contains a four-member ring of CoCoCN and II has a five-member of CoCoSCN.

Ｃｏ２ （ＣＯ）８ 与前配体（ＲＰＳ２ ）２ （Ｒ＝ Ｃ６Ｈ４ Ｏｐｈ，Ｃ６Ｈ４ＯＥｔ）反应，合成得到含前配体劈开的Ｓ与 ＳＰＲ 分子片的新颖六核钴羰合簇Ｃｏ６ （μ３－Ｓ）２ （ＣＯ）１４ （μ４－η２－ＳＰＣ６Ｈ４Ｏｐｈ）（Ⅰ）和Ｃｏ６ （μ３ －Ｓ）２（ＣＯ）１４ （μ４ －η２ －ＳＰＣ６ Ｈ４ ＯＥｔ）（Ⅱ）．对它们进行了元素分析，ＩＲ，１ＨＮＭＲ，３１ ＰＮＭＲ 和ＭＳ表征．该类簇合物有一个与四个金属原子相联的罕见的联硫磷ＳＰＲ 四齿桥基配体，它把两个等价的Ｃｏ３Ｓ（ＣＯ）７ 组块连结到一起，使整个分子外形似一飞雁．

Through the reaction of Co2(CO)8 with four thiuram [R2NC(S)S]2*,four new sulfur-capped trinuclear cobalt carbonyl clusters Co3(CO)7(μ3-S) (μ, η2-S*C*NR2) ( I : R= Me; II : R=Et; III : R=i-Pr; IV : NR= -N Hexagon sign], were prepared and characterized by elementary analysis, IR, 1H NMR and MS spectroscopy. The crystal structure of the cluster Co3(CO)7(μ3-S)[μ, η2-S*C*'N(i-Pr)2](III) was determined by X-ray single crystal diffraction method. The crystal of III is monoclinic, belonging to space group P21/n, and the cell parameters are as follows: a=1. 145 2(2) nm, b=1. 502 8(3) nm, c=1. 214 4(2) nm; α= 90°, β=92. 15(3)°, γ=90°; V=2. 088 5(7) nm3, Z=4, F(000)=1 096, Dc=1. 747 mg · m-3, μ=2. 588 mm-1, R=0.040 7, Rw=0. 062 4. The structural analysis shows that cluster III has a pyrimidal Co3S framework and contains a heterocylic bridging bidentate ligand[μ, η2-S*C*N(i-Pr)2] linked to the Co2 and Co3 atoms of the cluster by a cobalt-carbon and a cobalt-sulfur bond respectively.

Co2 (CO) 8 与 4个二硫代双 (烷基硫代甲酰胺 )类前配体 [R2 NC(S) S]2 反应 ,得 4个含烷基硫代甲酰胺基的三核钴羰基硫簇合物 .通过元素分析、IR、 1H NMR和 MS等方法表征了它们的结构 ,用 X射线衍射法测定了其中一个簇合物 Co3 (CO) 7(μ3 - S) [μ,η2 - SCN(i- Pr) 2 ]( )的晶体结构 .晶体属单斜晶系 ,P2 1/n空间群 ,晶胞参数 a=1.1452 (2 ) nm,b=1.50 2 8(3) nm,c=1.2 144 (2 ) nm,α=90°,β =92 .15(3)°,γ =90°,V =2 .0 885(7) nm3 ,Z=4 ,F (0 0 0 ) =10 96 ,Dc=1.74 7mg· m-3 ,GOF(F2 ) =0 .835,μ=2 .588nm-1.最终因子 R[I>2 σ(I) ]=0 . 0 4 0 7,Rw=0 .0 6 2 4

The title compound was obtained by the reaction of Rh-4 (CO)(12) with P(SC6H5)(3). The crystal structure of the compound has been determined by X-ray diffraction. The crystal system is monoclinic, space group P2(1)/a, a=17,390(8), b=8.983(9), C=24.35(2)angstrom, beta =103.8,1(4)degrees; V=3693(5)angstrom(3), Z=8, D-C=1.93g.cm(-3). R=0.057, R-W=0.064. The intramolecular Rh-Rh distances are 3.090 and 3.078 angstrom respectively.

The title compound was obtained by the reaction of Fe-2(CO)(12) with phosphorotrithious acid triphenyl ester P(SC6H6)(2). Ligand precursor P(SC6H6)(3) coordinated to the cluster by its cleaved fragments SC4H5 and P(SC4H5)(2). The crystal structure of the compound has been determined by a single crystal X-ray diffraction method. The crystal is orthorhombic, space group belongs Pbca,a=17.422(7), b=10.634(6), c=28.987(12), V=5370A(3), z=8, D-c=1.579g.cm(-1). Coordinates of all nonhydrogen atoms were determined by direct method and difference Fourier synthesis, with 3531 observable reflections (I >= 3a(I-0)) refined by a full-matrix least-squares procedure so that the final R=0.054, R-w=0>058. The dihedral angle of the folded Fe2SP ring along the S...P line or the Fe-Fe bond (76.1 degrees or 82 degrees, respectively,) is much smaller than that for other similar compounds with the central Fe2S2 or Fe2P2 of Fe-2. SP folded rings. Fe-Fe =2.572(2)A, Fe-S(1)-Fe=68.6 degrees(1), Fe-P-Fe=70.7 degrees(1).

九羰基二硫三铁是少有的稳定的铁羰簇合物中的一个.有时在输煤气管道中可以发现它的存在.簇中的铁与硫结合成强的Fe—S键,是形成对氮的固定起关键作用的铁硫蛋白结构的重要因素.它与P（OR） 3 (R=n-C 3 H 7 ,sec-C 4 H 9 ,cyclo-C 6 H 11 等)取代反应产物的晶体结构我们已有报导.本文报导它与P（SR）Cl 2 (R=C 6 H 5- ,C 2 H 5- ,C 3 H 7- )取代反应产物的晶体和分子结构.