含硫帽的三核和四核钌羰基簇合物的合成和结构表征

Synthesis, Characterization and Structures of Trinuclear and TetranuclearRuthenium Carbonyl Clusters Containing Capping S Atoms

The reaction of Ru3(CO)12 with five membered cyclic SP(S)(Fc)N(Ph)NC(Me) gave two novel trinuclear and tetranuclear ruthenium carbonyl clusters containing capping S atoms in Ru3(CO)8(μ 3 S)2[P(Fc)N(Ph)NC(Me)S] 1 and Ru4(CO)7(μ CO)3(μ 4 S)2[P(Fc)N(Ph)NC(Me)S] 2 (Fc=C5H5FeC5H4). During the reaction, the ligand precursor cleaved only in its P=S bond to give the fragments S and [P(Fc)N(Ph)NC(Me)S], and then coordinated to the ruthenium atoms to form the clusters as listed above. The clusters have been characterized by elementary analysis, IR, 1H NMR and MS spectroscopy. The crystal structure of cluster 2 has been determined by X ary diffraction techniques. The crystal belongs to monoclinic with space group P21/c. The unit cell parameters are as follows: a=1.18744(7) nm, b=1.36041(11) nm, c=2.20026(18) nm, β =104.126(3) ° , V=3.4468(5) nm3, Dc=2.175 g· cm- 3, Z=4. In the molecule, the three bridging carbonyls and Ru4 are planar and with a pseudo octahedral Ru4S2 skeleton. The terminal carbonyl of Ru1 was substituted by the cyclic ligand [P(Fc)N(Ph)NC(Me)S]. CCDC: 217076.

The reaction of Ru-3(CO)(12) with five-membered cyclic SP(S)(Fc)N(Ph)NC(Me) gave two novel trinuclear and tetranuclear ruthenium carbonyl clusters containing capping S atoms in Ru-3(CO)(8)(mu(s)-S)(2)[P(Fc)N(Ph)NC(Me)S], and Ru-4 (CO)(7)(mu-CO)(3)(mu(4)-S)(2) [P(Fc)N(Ph)NC(Me)S](2) (Fc = C5H5FeC5H4). During the reaction, the ligand precursor cleaved only in its P = S bond to give the fragments S and [P(Fc)N(Ph)NC(Me) S], and then coordinated to the ruthenium atoms to form the clusters as listed above. The clusters have been characterized by elementary analysis, IR, H-1 NMR and MS spectroscopy. The crystal structure of cluster 2 has been determined by X-ary diffraction techniques. The crystal belongs to monoclinic with space group P2(1)/ c. The unit cell parameters are as follows: a = 1.18744 (7) nm, b = 1. 36041 (11) nm, c = 2.20026 (18) nm, beta = 104. 126 (3)degrees, V = 3.4468 (5) = nm(3), D = 2.175 g . cm(-3), Z = 4. In the molecule, the three bridging carbonyls and Ru4 are planar and with a pseudo-octahedral RU4S2 skeleton. The terminal carbonyl of Ru1 was substituted by the cyclic ligand [P(Fc)N(Ph)NC(Me)S].