Synthesis and spectroscopic and X-ray structural characterisation of some para-substituted triaryltin(pentacarbonyl)manganese(I) complexes

A series of para-substituted triaryltin(pentacarbonyl)manganese(I) compounds [(p-XC6H4)3SnMn(CO)5: II, X=CH3; III, X=CH3O; IV, X=CH3S; V, X=F; VI, X=Cl; VII, X=CH3S(O2)] is reported for comparison with the known phenyl analogue I. IR data [ν(CO)] as well as complete 119Sn/55Mn/13C solution NMR results are given for I–VII. Chemical shifts, 119Sn versus 55Mn, except I, correlate well, but have differing single parameter (SP) correlations, 119Sn versus σI and 55Mn versus σ°p. These results are compared with previous SP studies of the 119Sn solution NMR spectra of the series, (p-XC6H4)4Sn and (p-XC6H4)3SnY (Y=Cl, Br, I). Full crystal structures are reported for compounds II–VI. All are similar to that of I, with the Mn(CO)5 moiety being a distorted tetragonal pyramid, and having a quasi-mirror plane through the central C4MnSnC3 skeleton. The Ar3Sn are distorted trigonal propellers with ring torsion angles in the range 30–80°, the exception being IV with one torsion angle of 22°.