(Hexamethylbenzene)ruthenium(II) complexes: synthesis and coordination chemistry of a novel tridentate ligand with an O,O,Cl donor set

Journal Article · Wed Oct 05 04:00:00 EDT 1988 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00293a014· OSTI ID:6236523

Klaeui, W; Buchholz, E

Trimethyl phosphite reacts with (((C/sub 6/Me/sub 6/)RuCl/sub 2/)/sub 2/) in methanol to yield the cation ((C/sub 6/Me/sub 6/)RuCl(P(OCH/sub 3/)/sub 3/)/sub 2/)/sup +/, which has been isolated as a chloride or hexafluorophosphate salt. This cation undergoes a sequence of two Michaelis-Arbuzov type reactions to give the neutral complex and the L/sup -/ anion ((C/sub 6/Me/sub 6/)RuCl(P(O)(OCH/sub 3/)/sub 2/)/sub 2/)/sup -/. Attempts to isolate the anion in the form of its sodium salt NaL have led to products that always contain additional sodium iodide or sodium hexafluorophosphate. The free acid HL can be prepared by protonation from NaL or directly from the reaction of (((C/sub 6/Me/sub 6/)RuCl/sub 2/)/sub 2/) with dimethyl phosphonate, HP(O)(OCH/sub 3/)/sub 2/. L/sup -/ is a uninegative, potentially bidentate or tridentate ligand with an O,O,Cl donor set. It reacts with many transition-metal and main-group-metal ions, e.g. M/sup n+/ = Mg/sup 2 +/, Mn/sup 2 +/, Co/sup 2 +/, Ni/sup 2 +/, Cu/sup 2 +/, Zn/sup 2 +/, Cd/sup 2 +/, Pb/sup 2 +/, Al/sup 3 +/, or Fe/sup 3 +/, to give 2:1 complexes of the composition (ML/sub 2/)/sup (n-2)+/. The reactions of the complexes (((ring)MCl/sub 2/)/sub 2/), (ring)M = (C/sub 5/Me/sub 5/)Rh, (C/sub 6/Me/sub 6/)Ru, and (p-cymene)Ru, with L/sup -/ lead to the cationic complexes ((C/sub 5/Me/sub 5/)RhL)/sup +/, ((C/sub 6/Me/sub 6/)RuL)/sup +/, and ((p-cymene)RuL)/sup +/, which have been isolated as hexafluorophosphate salts. HL oxidatively adds to the metal(0) complexes (Mo(CH/sub 3/CN)/sub 3/(CO)/sub 3/) and (W(DMF)/sub 3/(CO)/sub 3/) to yield metal hydride complexes of the composition (LM(CO)/sub 3/H). The molybdenum hydride is labile and rapidly gives HL and Mo(CO)/sub 6/ under an atmosphere of CO gas.

• Research Organization: Institut fuer Anorganische Chemie, Aachen (West Germany)
• OSTI ID: 6236523
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:20; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
AROMATICS
BARYONS
CARBONYLS
CHEMICAL PREPARATION
CHLORIDES
CHLORINE COMPOUNDS
DATA
ELEMENTARY PARTICLES
EXPERIMENTAL DATA
FERMIONS
HADRONS
HALIDES
HALOGEN COMPOUNDS
INFORMATION
ISOTOPES
LIGHT NUCLEI
NMR SPECTRA
NUCLEI
NUCLEONS
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
PHOSPHORUS 31
PHOSPHORUS ISOTOPES
PROTONS
REFRACTORY METAL COMPOUNDS
RUTHENIUM CHLORIDES
RUTHENIUM COMPOUNDS
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS