Synthese und Struktur der Nitridokomplexe (Ph₃Sb)₂Cl₃Os≡N-RhCl(COD), (Me₂PhP)₂(PhCN)Cl₂Re≡N-RhCl₂(C₅Me₅), [(Me₂PhP)₃(PhCN)ClRe≡N-OsCl₂(CO)₃][OsCl₃(CO)₃] und [(Me₂PhP)₃(PhCN)ClRe≡N-ReCl₄-N≡ReCl(NCPh)(PMe₂Ph)₃][OsCl₄(CO)₂] / Synthesis and Structure of the Nitrido Complexes (Ph₃Sb)₂Cl₃Os≡N-RhCl(COD), (Me₂PhP)₂(PhCN)Cl₂Re≡N-RhCl₂(C₅Me₅), [(Me₂PhP)₃(PhCN)ClRe≡N-OsCl₂(CO)₃][OsCl₃(CO)₃], and [(Me₂PhP)₃(PhCN)ClRe≡N-ReCl₄-N≡ReCl(NCPh)(PMe₂Ph)₃][OsCl₄(CO)₂]

Abstract

The reaction of (Ph 3 Sb) 2 Cl 3 OsN with [Rh(μ-Cl)(COD)] 2 in benzonitrile yields the heteronuclear nitrido complex (Ph 3 Sb) 2 Cl 3 Os≡N-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, α = 101.214(4), β = 92.923(8), γ = 92.836(5)֯, and Z = 2. The complex fragment RhCl(COD) is coordinated to the osmium nitrido complex via a linear nitrido bridge Os≡N-Rh, with a bond angle Os-N-Rh = 175.3(5)° and distances Os-N = 168.6(6) and Rh-N = 184.6(6) pm. The heteronuclear complexes (Me 2 PhP) 2 (PhCN)Cl 2 Re≡N-RhCl 2 (C 5 Me 5 ) (2) and [(Me 2 PhP) 3 (PhCN)ClRe≡NOsCl 2 ( CO) 3 ][OsCl 3 (CO) 3 ] (3) are obtained by the reaction of (Me 2 PhP) 3 Cl 2 ReN with [RhCl(μ- Cl)(C 5 Me 5 )] 2 and [OsCl(μ-Cl)(CO) 3 ] 2 , respectively, in benzonitrile. 2 forms orange red crystals with the composition 2・C 6 H 5 CN in the monoclinic space group P2 1 /c and a =910.23(7), b =1255.4(1), c = 3761.5(3) pm, β = 95.617(9)° and Z = 4. The nitrido bridge Re≡N-Rh to the complex fragment [RhCl 2 (C 5 Me 5 )] has a bond angle Re-N-Rh of 171.9(3)° and distances Re-N = 169.4(5) and Rh-N = 201.9(5) pm. 3 forms yellow orange plates with the monoclinic space group P2 1 /c and a = 1113.74(5), b = 2038.5(2), c = 2130.1(1) pm, β = 90.298(6)° and Z = 4. The nitrido bridge within the complex cation [(Me 2 PhP) 3 (PhCN)ClRe≡N-OsCl 2 (CO) 3 ] + is characterized by a bond angle Re-N-Os of 167.7(4)° and distances Re-N = 169.5(8) and Os-N = 206.1(8) pm. The ligands of the octahedral anion [OsCl 3 (CO) 3 ] − are in a facial arrangement. The synthesis of 3 yields [{(Me 2 PhP) 3 (PhCN)ClRe≡N} 2 ReCl 4 ][OsCl 4 (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, α =87.41(1), β =88.54(1), γ =62.453(8)° and Z =2. In the two symmetry independent, centrosymmetric cations [(Me 2 PhP) 3 (PhCN)ClRe≡N-ReCl 4 -N≡ReCl(NCPh)(PMe 2 Ph) 3 ] 2+ of 4 two nitrido complexes [(Me 2 PhP) 3 (PhCN)ClReN] + coordinate with their terminal nitrido ligands a central, square planar ReCl 4 unit. The resulting nitrido bridges with bond angles Re(1)-N(1)- Re(2) = 167.0(4)° and Re(3)-N(2)-Re(4) = 168.9(4)°, 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 [OsCl 4 (CO) 2 ] 2− are in cis position.