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 · Wed Feb 07 00:00:00 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]

---

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), Vol. 29:3; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

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