Synthesis and insertion chemistry of cationic zirconium(IV) pyridyl complexes. Productive. sigma. -bond metathesis

Journal Article · Tue May 01 00:00:00 EDT 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00119a029· OSTI ID:6379790

Jordan, R F; Taylor, D F; Baenziger, N C ^[1]

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1. Univ. of Iowa, Iowa City (USA)

The reaction of Cp{sub 2}Zr(CH{sub 3})(THF){sup +} (1) with pyridine produces CH{sub 4} and a mixture of Cp{sub 2}Zr({eta}{sup 2}-N,C-pyridyl)(THF){sup +} (2) and Cp{sub 2}Zr({eta}{sup 2}-N,C-pyridyl)(pyridine){sup +} (3) via ortho-C-H bond activation. Complex 2 is converted to 3 by reaction with excess pyridine. Complex 1 reacts similarly with 2-methylpyridine ({alpha}-picoline) to yield the picolyl complex Cp{sub 2}Zr({eta}{sup 2}-N,C-NC{sub 5}H{sub 3}(6-Me))(THF){sup +} (6). An intermediate picoline adduct Cp{sub 2}Zr(CH{sub 3})(picoline){sup +} (7a) is observed in this reaction. Low-temperature NMR studies of 7a and the (C{sub 5}H{sub 4}Me){sub 2}Zr analogue 7b reveal a high-field {sup 1}H shift and a reduced J{sub C-H} for the ortho C-H of the coordinated picoline suggestive of an agostic interaction. These Zr-mediated olefin/picoline coupling reactions illustrate how productive reaction schemes may be constructed by combining {sigma}-bond metathesis, insertion, and {beta}-H elimination reactions.

• DOE Contract Number: FG02-88ER13935
• OSTI ID: 6379790
• Journal Information: Organometallics; (USA), Vol. 9:5; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ZIRCONIUM COMPLEXES
SYNTHESIS
CATALYSIS
CHEMICAL ACTIVATION
DATA ANALYSIS
EXPERIMENTAL DATA
MEASURING INSTRUMENTS
MEASURING METHODS
METHANE
PYRIDINE
ALKANES
AZINES
COMPLEXES
DATA
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties