Reduction of carbon monoxide promoted by alkyl and hydride derivatives of permethylzirconocene

Journal Article · Wed Apr 26 04:00:00 EST 1978 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00477a025· OSTI ID:6745181

Manriquez, J M; McAlister, D R; Sanner, R D; Bercaw, J E

Bis(pentamethylcyclopentadienyl)dihydridozirconium(IV), (eta/sup 5/-C/sub 5/Me/sup 5/)/sub 2/ZrH/sub 2/ (2) is prepared by the reaction of H/sub 2/ with ((eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/ZrN/sub 2/)/sub 2/N/sub 2/ (1). 2 forms unstable adducts with PF/sub 3/ and CO at -80/sup 0/C. The carbonyl adduct (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/ZrH/sub 2/(CO) yields ((eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/ZrH)/sub 2/(OCH == CHO) and/or (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/ZrH(OCH/sub 3/), depending on reaction conditions. Carbonylation of (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/Zr(CH/sub 3/)/sub 2/, obtained from (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/ZrCl/sub 2/ and methyllithium, yields successively (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/Zr(CH/sub 3/)(CH/sub 3/CO) and (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/Zr(O(CH/sub 3/)C == C(CH/sub 3/)O). The zirconacyclopentane ecomplex (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/Zr(CH/sub 2/(CH/sub 2/)/sub 2/CH/sub 2/) (10) is prepared from 1 and ethylene. Carbonylation of 10 affords (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/Zr(H)-(OC == OH(CH/sub 2/)/sub 2/CH/sub 2/). Treatment of 2 with isobutylene yields (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/Zr(H)(Ch/sub 2/CHMe/sub 2/) (13), which undergoes a reaction with CO to form (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/Zr(H)(OCH == CHCHMe/sub 2/) (15). The results of /sup 13/C and deuterium labeling studies indicate that the conversion of 13 to 15 is mediated by (eta/sup 5/-C/sub 5/Me/sub 5/)/sub 2/Zr(H)(Me/sub 2/CHCH/sub 2/CO). The observed patterns for these reactions of alkyl and hydride derivatives of zirconium with CO are attributed to carbenoid character of the carbonyl carbon resulting from an unusual ''side-on'' coordination of acyl and formyl groups.

• Research Organization: California Inst. of Tech., Pasadena
• OSTI ID: 6745181
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 100:9; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKENES
CARBON 13
CARBON COMPOUNDS
CARBON ISOTOPES
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CATALYSTS
CHALCOGENIDES
CHEMICAL REACTIONS
CYCLOALKENES
CYCLOPENTADIENE
DEUTERIUM
DIENES
EVEN-ODD NUCLEI
HYDROCARBONS
HYDROGEN ISOTOPES
ISOTOPES
LABELLED COMPOUNDS
LIGHT NUCLEI
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
POLYENES
STABLE ISOTOPES
TRANSITION ELEMENT COMPOUNDS
ZIRCONIUM COMPOUNDS