Synthesis and structure of the nitrido complexes (Ph3Sb)2Cl3OsN-RhCl(COD), (Me2PhP)2(PhCN)Cl2ReN-RhCl2(C5Me5), [(Me2PhP)3(PhCN)ClReN-OsCl2(CO)3][OsCl3(CO)3], and [(Me2PhP)3(PhCN)ClReN-ReCl4-NReCl(NCPh)(PMe2Ph)3][OsCl4(CO)2]

The reaction of (Ph3Sb)(2)Cl3OsN with [Rh(mu-Cl)(C0D)](2) in benzonitrile yields the heteronuclear nitrido complex (Ph3Sb)(2)Cl(3)Osequivalent toN-RhCl(COD) (1). It crystallizes as dark brown blocks in the triclinic space group P1 with a = 1080.09(5), b = 1173.15(5), c = 1702.28(9) pm, alpha = 101.214(4), beta = 92.923(8), gamma = 92.836(5)degrees, and Z = 2. The complex fragment RhCl(COD) is coordinated to the osmium nitrido complex via a linear nitrido bridge Osequivalent toN-Rh, with a bond angle Os-N-Rh = 175.3(5)degrees and distances Os-N = 168.6(6) and Rh-N = 184.6(6) pm. The heteronuclear complexes (Me2PhP)(2)(PhCN)Cl(2)Reequivalent toN-RhCl2(C5Me5) (2) and [(Me2PhP)(3)(PhCN)CIReequivalent toN0OSCl(2)(CO)(3)][OsCl3(CO)(3)] (3) are obtained by the reaction of (Me2PhP)(3)Cl2ReN with [RhCl(mu-Cl)(C5Me5)](2) and [OSCI(P -Cl)(CO)312, respectively, in benzonitrile. 2 forms orange red crystals with the composition 2 (.) C6H5CN in the monoclinic space group P2(1)/c and a = 910.23(7), b = 1255.4(1), c = 3761.5(3) pm, beta = 95.617(9)degrees and Z = 4. The nitrido bridge Reequivalent toN-Rh to the complex fragment [RhCl2(C5Me5)] has a bond angle Re-N-Rh of 171.9(3)degrees and distances Re-N = 169.4(5) and Rh-N 201.9(5) pm. 3 forms yellow orange plates with the monoclinic space group P211c and a = 1113.74(5), b = 2038.5(2), c = 2130.1(1) pm, beta = 90.298(6)degrees and Z = 4. The nitrido bridge within the complex cation [(Me2PhP)(3)(PhCN)ClReequivalent toN-OSCl2(CO)(3)1](+) is characterized by a bond angle Re-N-Os of 167.7(4)degrees and distances Re-N = 169.5(8) and Os-N = 206.1(8) pm. The ligands of the octahedral anion [OsCl3(CO)(3)](-) are in a facial arrangement. The synthesis of 3 yields [{(Me2PhP)(3)(PhCN)ClReequivalent toN}(2) ReCl4][OSCl4(CO)(2)] (4) as a byproduct. It crystallizes as red brown blocks with the composition 4(.)CH(2)Cl(2) in the space group P1 and a = 1444.2(1), b = 1536.3(1), c = 2150.5(2) pm, alpha = 87.41 (1), beta = 88.54(1), gamma = 62.453(8)degrees and Z = 2. In the two symmetry independent, centrosymmetric cations [(Me2PhP)(3)(PhCN)ClReequivalent toN-ReCl4-Nequivalent toReCl(NCPh)(PMe2Ph)(3)](2+) of 4 two nitrido complexes [(Me2PhP)(3)(PhCN)ClReN](+) coordinate with their terminal nitrido ligands a central, square planar ReCl4 unit. The resulting nitrido bridges with bond angles Re(1)-N(1)-Re(2) = 167.0(4)degrees and Re(3)-N(2)-Re(4) = 168.9(4)degrees, respectively, exhibit distances Re(1)-N(1) = 172.4(7) and Re(2)-N(1) = 197.1(7) or Re(3)-N(2) = 171.4(6) and Re(4)-N(2) = 197.1(6) pm. The two carbonyl ligands of the anion [OsCl4(CO)(2)](2-) are in cis position.