Synthesis of molybdenum imido alkylidene complexes and some reactions involving acyclic olefins

Journal Article · Tue May 08 20:00:00 EDT 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00166a023· OSTI ID:6811997

Schrock, R R; Murdzek, J S; Bazan, G C; Robbins, J; DiMare, M; O'Regan, M ^[1]

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1. Massachusetts Institute of Technology, Cambridge (USA)

The reaction between Mo(C-t-Bu)(dme)Cl{sub 3} (dme = 1,2-dimethoxyethane) and Me{sub 3}SiNHAr (Ar = 2,6-diisopropylphenyl) yields Mo(C-t-Bu)(NHAr)Cl{sub 2}(dme) (1), which upon treatment with a catalytic amount of NEt{sub 3} is transformed into Mo(CH-t-Bu)(NAr)Cl{sub 2}(dme) (2). Complexes of the type Mo(CH-t-Bu)(NAr)(OR){sub 2} (OR = OCMe(CF{sub 3}){sub 2}, OCMe{sub 2}(CF{sub 3}), O-t-Bu, or OAr) have been prepared from 2. Complexes of the type Mo(C-t-Bu)(NHAr)(OR){sub 2} (OR = OCMe(CF{sub 3}){sub 2} or OAr) have been prepared from 1, but they cannot be transformed into Mo(CH-t-Bu)(NAr)(OR){sub 2} complexes. A precursor to imido alkylidene complexes that is related to 2 has been prepared by the sequence MoO{sub 2} {yields} MoO{sub 2}Cl{sub 2} {yields} Mo(NAr){sub 2}Cl{sub 2} {yields} Mo(NAr){sub 2}(CH{sub 2}R{prime}){sub 2} {yields} Mo(CHR{prime})(NAr)(OTf){sub 2}(dme) (R{prime} = t-Bu or CMe{sub 2}Ph; OTf = OSO{sub 2}CF{sub 3}). Mo(CH-t-Bu)(NAr)(OTf){sub 2}(dme) crystallizes in the space group P{anti 1} with a = 17.543 {angstrom}, b = 19.008 {angstrom}, c = 9.711 {angstrom}, {alpha} = 91.91{degree}, {beta} = 99.30{degree}, {gamma} = 87.27{degree}, Z = 4, M{sub r} = 729.60, V = 3,191.1 {angstrom}{sup 3}, {rho}(calcd) = 1.518 g cm{sup {minus}3}.

• DOE Contract Number: FG05-86ER75292
• OSTI ID: 6811997
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:10; 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
ALKENES
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
MOLYBDENUM COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES