Synthesis of five- and six-coordinate alkylidene complexes of the type Mo(CHR)(NAr)[OCMe(CF[sub 3])[sub 2]][sub 2]S[sub x] and their use as living ROMP initiators or wittig reagents

Journal Article · Mon Mar 01 00:00:00 EST 1993 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00027a028· OSTI ID:6153188

Fox, H H; Lee, J K; Park, L Y; Schrock, R R ^[1]

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1. Massachusetts Inst. of Technology, Cambridge (United States)

Addition of a slight excess of 4-methoxy-1-hexene to Mo(CHCMe[sub 2]Ph)(NAr)(OR[sub F6])[sub 2] (1a) or Mo(CHCMe[sub 3])(NAr)(OR[sub F6])[sub 2] (1b) in pentane (OR[sub F6] = OCMe(CF[sub 3])[sub 2]) yielded crystalline, red-orange anti-Mo[CHCH[sub 2]CH(OMe)CH[sub 2]CH[sub 3]](NAr)(OR[sub F6])[sub 2] (2). A similar reaction was used to prepare the difunctional complex anti-[(ArN)(OR[sub F6])[sub 2]Mo=CHCH[sub 2]CH(OMe)][sub 2]C[sub 6]H[sub 4] (3). Styrene reacts with 1a or 1b in DME over a period of 12 h to afford orange syn-Mo(CHPh)(NAr)-(OR[sub F6])[sub 2](DME) (4) in good yield. 4-(Dimethylamino)styrene and 2,4,6-trimethyoxystyrene react analogously to yield dark red syn-Mo(CH-4-C[sub 6]H[sub 4]-NMe[sub 2])(NAr)(OR[sub F6])[sub 2] (DME) (5) and red anti-Mo[CH-2,4,6-C[sub 6]H[sub 2]-(OMe)[sub 3]](NAr)(OR[sub F6])[sub 2](D ME) (6). 4 also can be synthesized from Mo-(NAr)[sub 2](DME) via Mo(NAr)[sub 2](CH[sub 2]Ph)[sub 2] and Mo(CHPh)(NAr)(OTf)[sub 2](DME). The reaction between 1 and 0.5 equiv of octatetraene in DME afforded syn-(DME)(R[sub F6]O)[sub 2](ArN)Mo(CH)[sub 6]Mo(NAr)(OR[sub F6])[sub 2](DME) (9a). A related complex, syn-(Et[sub 2]O)(R[sub F6]O)[sub 2](ArN)Mo(CH)[sub 6]Mo(NAr)(OR[sub F6])[sub 2](Et[sub 2]O) (9b), could be prepared directly in diethyl ether or by dissolving 9a in diethyl ether. anti-(THF)(R[sub F6]O)[sub 2](ArN)Mo(CH)[sub 6]Mo(NAr)(OR[sub F6])[sub 2](THF) (9c) was observed upon dissolving 9a in THF. The techniques described here should expand the opportunities for making polymers via living ROMP reactions and, in particular, should allow one to introduce conjugated sequences with a known, fixed length into a variety of polymers and to attach functional groups to both ends of a polymer. 41 refs., 1 fig., 3 tabs.

• DOE Contract Number: FG02-86ER13564
• OSTI ID: 6153188
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 12:3; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360601 -- Other Materials-- Preparation & Manufacture
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALDEHYDES
ALKYLATED AROMATICS
AROMATICS
CATALYSTS
CHEMICAL REACTIONS
COMPLEXES
DIVINYLBENZENE
HYDROCARBONS
MAGNETIC RESONANCE
MOLYBDENUM COMPLEXES
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
POLYMERIZATION
RESONANCE
STYRENE
SYNTHESIS
TRANSITION ELEMENT COMPLEXES