The reaction of Ru3(CO)12 with P(NEt2)2Cl, yields two trinuclear ruthenium carbonyl clusters: HRu3(CO)9[ μ3-η2-P(NEt2)2]2 Ⅰ (known) and a novel Ru3(CO)7( μ-Cl)2[ μ-P(NEt2)2]2 Ⅱ. During the reaction, the ligand precursor was cleaved in its P-Cl bond to give the fragments Cl and P(NEt2)2, and then coordinated to the ruthenium atoms to form the clusters as listed above. The crystal structure of cluster Ⅱ has been determined by X-ray diffraction technique. The crystal belongs to monoclinic with space group P21 / c. The unit cell parameters are as follows: a=1.287 9(6) nm, b=1.653 9(8) nm, c=1.643 6(8) nm, β=95.786(7)°, V=3.483(3) nm3, Dc=1.756 g·cm-3, Z=4. The cluster has a closed triangle Ru3 framework. Two Ru-Ru bonds are supported by μ-P(NEt2)2, the other one is connected by double Cl bridging. The valence electrons of the cluster are 50e. CCDC: 231979.
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.
