Absolute configurations of organometallic compounds. Part 6. The crystal structure and absolute configuration of (–)₅₇₈-carbonyl(η-cyclopentadienyl){[(S)-methyl(1-phenylethyl)amino]diphenylphosphine}-nitrosylmolybdenum

Optically active transition-metal complexes. 85. The BF3-promoted carbonylation of CpFe(CO)(L)Me compounds - a reaction stereospecific at low temperatures

“…In our preliminary communication26 the configurational correlation between (-)436-starting material (the present IBS) and (-)436-carbonylation product (the present 2SS) was based on the CD spectra, because the absolute configurations of the optically active iron methyl and acetyl compounds were unknown. Three types of correlations -27(5) N 0.6146 (5) 0.0904 (4) 0.4319 (5) 24 (4) 27 (4) 51 (5) -6 (3) 8(4) 0(4) C(6) 0.4728 (8) -0.1236 (7) 0.3258 (7) 46 (6) 32 (5) 70 ( 7 C(l) 0.5260 (6) -0.2581 (4) 0.4680 (5) 77 (3) H(5) 0.6832 (6) -0.1967 (4) 0.4383 (5) 70 (0) C(2) 0.4480(6) -0.2325 (4) 0.5380 (5) 60 (3) H(7A) 0.2737 (5) -0.0864 (7) 0.5170 (8) 70 (0) C(3) 0.4897 (6) -0.1542 (4) 0.5920 (5)…”

Recent organometallic nitrosyl chemistry

“…One of these, complex 6, has a metal atom that is a stereogenic center. 26 The RMo and SMo complexes27 are separable by preparative liquid chromatography. Reactions of 4 with NOC1 yield CpM(NO)2Cl complexes.12,16,28 These dinitrosyl chloro compounds are also obtainable from the treatment of the corresponding tricarbonyl dimers (M = Mo, W)29 with NOC1 or from exposure of the (cyclopentadienyl)metal dichloride to nitric oxide.…”

Reversible migration of an axial carbene ligand into an iron-nitrogen bond on a porphyrin. Implications for high oxidation states of heme enzymes and heme catabolism

“…*1 and have shown that these are oxidized to the species of composition [(p-ClC6H4)2C=C:]-FeTPPY (2).10 The oxidized form 2 may be readily reduced to re-form 1. Here we demonstrate that this involves reversible carbene migration coupled to the redox reaction as shown in eq 1.…”