Metal promoted alkyl migration in a bimetallic complex

Boryls Bound to Iron Carbonyl. Structure of a Rare Bis(boryl) Complex, Synthesis of the First Anionic Boryl, and Reaction Chemistry That Includes the Synthetic Equivalent of Boryl Anion Transfer

“…In a fashion similar to the trends in 11 B NMR chemical shifts for 1 − 6 , the 13 C NMR chemical shifts corresponding to the carbonyl groups of anionic compounds 4 − 6 were 15−20 ppm downfield of those for neutral 1 − 3 . Such downfield shifts of the 13 C resonances of carbonyl groups in other anionic complexes relative to their neutral counterparts have been observed. , The presence of a single resonance shows that the carbonyl groups are undergoing rapid site exchange, a process that is characteristic of five-coordinate compounds. − At −80 °C in toluene solvent, the resonance for 6 broadened but was not resolved into two separate signals.…”

Hydrogénation of phosphido bridged ruthenium clusters. A view of P—C bond activation and cleavage in the coordinatively unsaturated molecule Ru3(CO)9(μ2-PPh2)(μ2-H): conversion of μ2-PPh2 to μ3-PPh

“…Considerable attention has recently focussed on the synthesis and catalytic behaviour of phosphido (PR,) (2) and phosphinidene (PR) (3) based carbonyls since these groups have a number of features desirable in edge bridging or face capping ligands (4). Two rather notable examples are the use of the dianion Fe2(CO),(PPh2),L-in the synthesis of aldehydes from alkyl halides ( 5 ) and the catalytic hydroformyiating ability of the phos-ITo whom all correspondence should be addressed. phinidene complex C O~( C O )~(~~-C O )~(~~-P P~ (6).…”

First-Row Transition-Metal-Catalyzed Carbonylative Transformations of Carbon Electrophiles

“…Tertiary alkyl halides were not tolerated, and secondary tosylates gave higher yields than secondary halides. Collman investigated the mechanism of oxidative addition alkyl halides and tosylates to Na 2 Fe­(CO) 4 and the alkyl migration of [RFe­(CO) 4 ] − − in detail and reviewed its application in organic synthesis . In addition, the Na 2 Fe­(CO) 4 -mediated synthesis of hemifluorinated ketones using perfluoroalkyl halides was also reported …”