High oxidation state monopentamethylcyclopentadienyl tungsten methyl complexes including the first d/sup 0/ complex containing a highly distorted methylene ligand, W(eta/sup 5/-C/sub 5/Me/sub 5/)(CH/sub 3/)/sub 3/(CH/sub 2/)

Journal Article · Wed Jul 08 00:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00248a024· OSTI ID:5890462

Liu, A H; Murray, R C; Dewan, J C; Santarsiero, B D; Schrock, R R

Mono-eta/sup 5/-C/sub 5/H/sub 5/ complexes are among the most common in organometallic chemistry. After pentamethylcyclopentadiene became readily available, many mono-eta/sup 5/-C/sub 5/Me/sub 5/ analogues were prepared and their chemistry compared with that of known eta/sup 5/-C/sub 5/H/sub 5/ complexes. Soon mono-eta/sup 5/-C/sub 5/Me/sub 5/ (Cp*) complexes were discovered that had no eta/sup 5/-C/sub 5/H/sub 5/ analogues, e.g., TaCp*(olefin)Cl/sub 2/ and IrCp*H/sub 2/(SiMe/sub 3/)/sub 2/. Such a circumstance appears to be more common when the metal is in a relatively high oxidation state. One of the likely reasons the Cp* ligand apparently stabilizes high oxidation states is its now well-documented ability to donate electron density to the metal. Another important reason is that decomposition pathways involving eta/sup 5/-C/sub 5/H/sub 5/ ring protons are blocked. Relatively recently the authors discovered that (W(eta/sup 5/-C/sub 5/Me/sub 4/-t-Bu)Cl/sub 4/)/sub 2/ was a product of the reaction between the tungstacyclobutadiene complex W(C(t-Bu)C(Me)C(Me))Cl/sub 3/ and 2-butyne. They soon developed a practical route to the eta/sup 5/-C/sub 5/Me/sub 5/ analog and found that WCp*Me/sub 4/ could be prepared readily. They were interested in WCp*Me/sub 4/ first as a means of preparing hydride complexes such as (WCp*H/sub 3/)/sub 4/ and (WCp*H/sub 4/)/sub 2/, but then they became interested in exploring its chemistry per se. In this paper they report the first collection of results concerning the chemistry of WCp*Me/sub 4/ and related methyl complexes.

• Research Organization: Massachusetts Institute of Technology, Cambridge
• DOE Contract Number: AC02-78ER04949
• OSTI ID: 5890462
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:14; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKENES
CHEMICAL PROPERTIES
COMPLEXES
CYCLOALKENES
DATA
DIENES
EXPERIMENTAL DATA
HYDROCARBONS
HYDROGEN 1
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
LIGANDS
LIGHT NUCLEI
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
POLYENES
RESONANCE
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
VALENCE
VOLTAMETRY