Organo-f-element thermochemistry. Absolute metal-ligand bond disruption enthalpies in bis(pentamethylcyclopentadienyl)samarium hydrocarbyl, hydride, dialkylamide, alkoxide, halide, thiolate, and phosphide complexes. Implications for organolanthanide bonding and reactivity

Journal Article · Mon Nov 27 04:00:00 EST 1989 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00202a027· OSTI ID:6724663

Nolan, S P; Stern, D; Marks, T J ^[1]

---

1. Northwestern Univ., Evanston, IL (USA)

Absolute samarium-ligand bond disruption enthalpies in the series Cp{prime}{sub 2}Sm-R/X (Cp{prime} = {eta}{sup 5}-(CH{sub 3}){sub 5}C{sub 5}) have been measured by iodinolytic and alcoholytic isoperibol titration calorimetry of Cp{prime}{sub 2}Sm/(Cp{prime}{sub 2}Sm-I){sub n}, (Cp{prime}{sub 2}Sm-O{sup t}Bu){sub 2}/Cp{prime}{sub 2}Sm-R/X ensembles in toluene. A variety of Sm-centered ligand transposition and oxidative addition/reductive elimination processes are analyzed in light of the present data. The formation of strong Sm-heteroelement bonds makes an important contribution to the driving force. Hydrocarbon functionalization via dinuclear Sm(II) {yields} Sm(III) oxidative addition processes is only expected to be exothermic in special cases.

• OSTI ID: 6724663
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:20; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BONDING
CALCULATION METHODS
COMPLEXES
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
FABRICATION
INFORMATION
JOINING
LIGANDS
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
RARE EARTH COMPLEXES
REACTIVITY
SAMARIUM COMPLEXES
THERMOCHEMICAL PROCESSES