Effects on Coordination of Thioether Sites. 4. Structural Analysis of η 3 ‐Tripodal Ligand Manganese(I) Complexes

Crystal structures of a series of manganese(I) complexes containing tripodal ligands were determined. For [η 3 ‐{CH 3 C(CH 2 PPh 2 ) 2 (CH 2 SPh)‐ P,P′,S }Mn(CO) 3 ]PF 6 ( 1 ): a = 10.856(3) Å, b = 19.698(3) Å, c = 17.596(5) Å, β = 96.17(2)°, monoclinic, Z = 4, P2 1 /c, R(F o ) = 0.068, R w (F o ) = 0.055 for 3617 reflections with I o > 2σ(I o ). For [η 3 ‐{CH 3 C(CH 2 PPh 2 )(CH 2 SPh) 2 ‐ P,P′,S }Mn(CO) 3 ]PF 6 ( 2 ): a = 9.890(2) Å, b = 20.403(4) Å, c = 10.269(3) Å, β = 117.44(2)°, monoclinic, Z = 2, P2 l , R(F o ) = 0.050, R w (F o ) = 0.037 for 1760 reflections with I o > 2σ(I o ). For [η 3 ‐{CH 3 C(CH 2 PPh 2 ) 2 (CH 2 S)‐ P,P′,S }Mn(CO) 3 ] ( 4 ): a = 8.191(7) Å, b = 10.495(3) Å, c = 19.858(6) Å, α = 99.61(2)°, β = 96.17(2)°, γ = 92.70(4)°, triclinic, Z = 2, P‐I, R(F o ) = 0.048, R w (F o ) = 0.039 for 2973 reflections with I o > 2σ(I o ). There is no significant difference in the bond lengths of Mn‐S bonds among three species in their crystal structures [2.325(2) Å in 1; 2.358(4) in 2; 2.380(2) in 4], but the better donating ability of thiolate in complex 4 appears on the lower frequencies of its carbonyl stretching absorptions.