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The IR and NMR spectra of the complexes [M(CO) 6 ]Cl · HCl (M = Mn: 1, M = Re: 2), M(C0) 5 C0 2 Et (M = Mn: 3, M = Re: 4), [Mn(CO) 5 PR 3 ][PF 6 ] (5; PR 3  = PPh(OPh) 2 : a, P(n-Pr) 3 : b, PHPh 2 : c, PPh(NEt 2 ) 2 : d, P(p-C 6 H 4 F) 3 : e), [Re(CO) 5 PHPh 2 ][PF 6 ] (6 c), Mn 2 (CO) 8 (PR 3 ) 2  (7) and Re 2 (CO) 8 (PHPh 2 ) 2  (8c) are discussed in the context of σ-and π-interactions in the metal-ligand system and compared with  51 V NMR data of the analogous isoelectronic and isostructural carbonylvanadates (-I). On the basis of these results, the phosphines are arranged in the order of decreasing integral ligand strength according to a&gt;b&gt;c&gt;d. The  55 Mn shielding of 5 is greater than that of 1, which is explained by strong σ-interactions and correspondingly large e-a 1*  splitting dominating the paramagnetic deshielding term in the pseudooctahedral complexes of type 5. The only rhenium compound accessible to NMR is 2, for which the  185  Re and  187  Re resonances were obtained.  31 P coordination shifts are positive for all complexes. Spectroscopic data for 7c show that this complex presumably has the structure (CO) 5 Mn-Mn(CO) 3 (PHPh 2 ) 2 , contrasting 7a, 7b, 7d and 7e (local D 4d  symmetry).

zeitschrift für naturforschung b

IR,  31 P-,  55  Mn-und  185,187  Re-NMR spektroskopische Untersuchungen an einigen Carbonylmangan-und -rhenium-Komplexen/IR,  31 P,  55 Mn and  185,187 Re NMR Spectroscopic Investigations of Some Carbonylmanganese and -rhenium Complexes