(Chloromethyl)pentacarbonylmanganese(I): a crystal structure with a non-crystallographic centre of symmetry

Abstract

There are two molecules in the asymmetric unit of the P2 1 /c unit cell ClCH 2 Mn(CO) 5 , the first halomethyl complex of manganese to be structurally determined. The molecules are crystallographically independent, despite an apparent local centre of symmetry. The average bond parameters include Mn-C alkyl 2.128(8) Å, C-Cl 1.811 (8) Å and Mn-C-Cl 116.7(4)°.

Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

“…[28] The distance in [(CO) 5 Mn(CH 2 Cl)], which has one a-Cl substituent, is 2.125 (10) . [29] These data suggest that electronegative substituents (particularly F, but even Cl), even when placed on the b-C atom as in compound 7,s trengthen the MnÀCb ond, which is in agreement with the recent DFT study. [18] Infraredc haracterization…”

“…For comparison, other distances to the sp 3 ‐hybridized C atoms without any F substituents are 2.214(3) Å in [(CO) 5 Mn(CH 2 CH=CHCOOPh)] and 2.195(6) and 2.196(8) Å in [(CO) 5 Mn(CH 2 CH 2 ‐ o ‐C 6 H 4 −CH 2 CH 2 )Mn(CO) 5 ], whereas positional disorder in the simpler reference compound [(CO) 5 Mn(CH 3 )] prevented an accurate determination of the Mn−CH 3 distance . The distance in [(CO) 5 Mn(CH 2 Cl)], which has one α‐Cl substituent, is 2.125(10) Å . These data suggest that electronegative substituents (particularly F, but even Cl), even when placed on the β‐C atom as in compound 7 , strengthen the Mn−C bond, which is in agreement with the recent DFT study…”

Interplay of thermochemistry and Structural Chemistry, the journal (volume 19, 2008) and the discipline

“…Further, Nicholson et al [172] determined the crystal structure of (chloromethyl)pentacarbonylmanganese(I), the first halomethyl complex of manganese to be structurally determined. The structure has a noncrystallographic symmetry, and the equatorial manganese carbonyl groups are bent toward the alkyl group.…”