부산대학교 도서관

The reaction of the title compound with the metal carbonyls Cr(CO)5THF, Cr(CO)4C7H8, Mo(CO)4C7H8 and [Rh(CO)2Cl]2 resulted in the formation of the metal complexes P2[meNC(O)NmeCr(CO)5]2 7, P4[meNC(O)Nme]4 [Cr(CO)2 10, P4[meNC(O)Nme]4 [Mo(CO)4]2] 11 and P4[meNC(O)Nme]4 [Rh(CO)Cl]2 12. Under the reaction condition described no oxidative cleavage of the phosphorus-phosphorus-bond was observed. 10, 11, and 12 form six-membered rings containing four phosphorus and two metal atoms. The Lewis acids SnCl4 and SbCl5 react with the bicyclic biphosphine under formation of 1:1 P2[meNC(O)Nme]2SnCl4 8 and 2:1 P2[meNC(O)Nme]2(SbCl5)2 9 adducts. The structures of chromium-pentacarbonyl complex P2[meNC(O)Nme]2Cr(CO)5 6 and bis(chromiumtetracarbonyl)-bis(μ-2,4,6,8-tetramethyl-2,4,6,8-tetraaza-1Λ4-5Λ4-diphospha-bicyclo[3.3.0]octan-3,7-dione] 10 has been determined by single-crystal X-ray diffraction. 6 crystallizes in the monoclinic space group P21/c with unit cell constants a = 13.003(3), b = 9.924(2), c = 14.577(3) Å, β = 109.83(1)° and Z = 4. Full-matrix least-squares refinement of the structure converged with R = 0.078 and R = 0.066 for 1615 reflections with I > 2.0 σ(I). 10 crystallizes in the orthorhombic space group Pnma with unit cell constants a = 11.270(1), b = 19.497(3), c = 14.389(4) Å and Z = 4. Full-matrix least-squares refinement vielded the terminal values R = 0.108 and R = 0.091 for 717 reflections with I > 2.0σ(I). The Λ 3P-Λ4P and Λ4P-Λ4P distances in 6 and 10 respectively are similar [2.217(4) and 2.22(1) Å].