79190-85-5Relevant academic research and scientific papers
Structural characterization of tridentate 11-membered phosphino macrocyclic complexes of transition metals. Examples of octahedral, square-pyramidal, and tetrahedral geometries
Kyba, Evan P.,Davis, Raymond E.,Liu, Shiuh-Tzung,Hassett, Karen A.,Larson, Steven B.
, p. 4629 - 4634 (2008/10/08)
Three structures of 11-membered phosphino macrocyclic complexes of transition metals have been determined: tri(carbonyl-κC)[meso-cis-6-methyl-2,10-diphenyl-6-aza-κN-2,10- diphospha-κ 2P-bicyclo[9.4.0]pentadeca-11(1),12,14-triene]molydenum(0) (3a, C28H29MoNO3P2·0-5C 6H5CH3), tri(carbonyl-κC) [meso-cis-2,6,10-triphenyl-2,6,10-triphospha-κ 3P-bicyclo[9.4.0]pentadeca-11-(1),12,14-triene]tungsten(0) (3b, C33H31O3P3W), and dichloro[meso-cis-2,10-diphenyl-6-aza-κN-2,10-diphospha-κ 2P-bicyclo-[9.4.0]pentadeca-11(1),12,14-triene]nickel(II) (4, C24H27Cl2NNiP2). Structures 3a,b are fac octahedral, and 4 is square pyramidal with the NH moiety in the apical position. These structures are compared with each other and with another described previously, chloro[meso-cis-2,10-diphenyl-2,10-diphospha-κ 2P-6-thia-κS-bicyclo[9.4.0]penta-11(1),12,14-triene]copper(I) (5), which is approximately tetrahedral. Unusually long metal-nitrogen bond lengths are observed for 3a (Mo-N = 2.428 (3) A?) and for 4 (Ni-N = 2.428 (3) A?). The conformations of the trimethylene strands joining the heteroatoms in the coordinated macrorings are analyzed, and explanations are proposed for the observation of chair-chair conformations for the two 6-membered rings WPCH2CH2CH2P in 3b and the two 6-membered rings CuPCH2CH2CH2S in 5 but chair-boat conformations for the two 6-membered rings MoPCH2CH2CH2N in 3a and the two 6-membered rings NiPCH2CH2CH2N in 4. X-ray data were collected on a Syntex P21 autodiffractometer and refined by the full-matrix least-squares method. For 3a from toluene (as 3a·1/2C7H8), a = 10.083 (1) A?, b = 17.509 (3) A?, c = 9.082 (1) A?, α = 96.36 (1)°, β = 112.70 (1)°, γ = 77.89 (1)°, triclinic, P1, Z = 2, and R1 = 0.0314, R2 = 0.0322 for 5647 reflections with |Fo| > 4σ|Fo|. For 3b, a = 12.366 (1) A?, b = 15.436 (2) A?, c = 16.867 (2) A?, β = 103.914 (8)°, monoclinic, P21/c, Z = 4, and R1 = 0.0365, R2 = 0.0364 for 4761 reflections with |Fo| > 4σ|Fo|. For 4, a = 9.240 (1) A?, b = 15.474 (3) A?, c = 9.035 (2) A?, α = 96.90 (2)°, β = 67.38 (2)°, γ = 111.69 (1)°, triclinic, P1, Z = 2, and R1 = 0.0348, R2 = 0.0349 for 4136 reflections having |Fo| > 4σ|Fo|.
