Synthesis and properties of chiral rhenium ether complexes of the formula ((. eta. sup 5 -C sub 5 H sub 5 )Re(NO)(PPh sub 3 )(OR sub 2 )) sup + X sup minus

Journal Article · Tue Feb 06 23:00:00 EST 1990 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00328a027· OSTI ID:6902574

Agbossou, S K; Fernandez, J M; Gladysz, J A ^[1]

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1. Univ. of Utah, Salt Lake City (USA)

Reaction of the dichloromethane complex (({eta}{sup 5}-C{sub 5}H{sub 5})Re(NO)(PPh{sub 3})(ClCH{sub 2}Cl)){sup +}BF{sub 4}{sup {minus}} (2{sup +}BF{sub 4}{sup {minus}}; in CH{sub 2}Cl{sub 2}) and tetrahydrofuran gives (({eta}{sup 5}-C{sub 5}H{sub 5})Re(NO)(PPh{sub 3})(THF)){sup +}BF{sub 4}{sup {minus}} (5{sup +}BF{sub 4}{sup {minus}}; 91% after workup). Reaction of 2{sup +}BF{sub 4}{sup {minus}} and methyl ether gives (({eta}{sup 5}-C{sub 5}H{sub 5})Re(NO)(PPh{sub 3})(OMe{sub 2})){sup +}BF{sub 4}{sup {minus}} (4{sup +}BF{sub 4}{sup {minus}}, characterized in situ). Ethyl ether and 2{sup +}BF{sub 4}{sup {minus}} react to give (({eta}{sup 5}-C{sub 5}H{sub 5})Re(NO)(PPh{sub 3})(OEt{sub 2})){sup +}BF{sub 4}{sup {minus}} (3{sup +}BF{sub 4}{sup {minus}}), but not under preparatively useful conditions. Reaction of the hydride complex ({eta}{sup 5}-C{sub 5}H{sub 5})Re(NO)(PPh{sub 3})(H) (6), Ph{sub 3}C{sup +}PF{sub 6}{sup {minus}}, and tetrahydrofuran gives 5{sup +}PF{sub 6}{sup {minus}} (90%). Reaction of 6, Ph{sub 3}C{sup +}PF{sub 6}{sup {minus}}, and ethyl ether gives 3{sup +}PF{sub 6}{sup {minus}} (93%). Reactions of alkoxide complexes ({eta}{sup 5}-C{sub 5}H{sub 5})Re(NO)(PPh{sub 3})(OR) and oxonium salts R{sub 3}O{sup +}X{sup {minus}} (R = Et, Me) in CH{sub 2}Cl{sub 2} give ethers R{sub 2}O and ether complexes 3{sup +}x{sup {minus}}/4{sup +}X{sup {minus}} in quantitative NMR yields. These and other data show that tetrahydrofuran, methyl ether, and ethyl ether have higher thermodynamic binding affinities than dichloromethane for the metal fragment (({eta}{sup 5}-C{sub 5}H{sub 5})Re(NO)(PPh{sub 3})){sup +} and that the oxygen lone-pair basicity in ({eta}{sup 5}-C{sub 5}H{sub 5})Re(NO)(PPh{sub 3})(OR) is greater than that in R{sub 2}O. 24 refs.

• OSTI ID: 6902574
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 29:3; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BORON COMPOUNDS
BORON FLUORIDES
CHIRALITY
COMPLEXES
DATA
ETHERS
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
FURANS
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
PARTICLE PROPERTIES
RHENIUM COMPLEXES
SYNTHESIS
TETRAHYDROFURAN
TRANSITION ELEMENT COMPLEXES