Preparation and reactions of half-sandwich rhenium nitrosyl complexes containing a tethered amino ligand

Wang, Tein‐Fu; Lai, Ching-Yih; Wen, Yuh‐Sheng

doi:10.1016/0022-328x(96)06414-5

Cited by 11 publications

(5 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The 1 H NMR spectrum of 1·HCl showed the N -methyl protons at 2.86 ppm, while those of the free ligand C 5 H 5 (CH 2 ) 2 NMe 2 were measured at 2.27 ppm. Similar downfield shifts of the N -methyl protons have been observed in the titanium, molydenum, rhenium, and rhodium complexes containing similar ligands. Protonation of the amine group in 1·HCl was also supported by observation of the broad singlet signal of N−H at 12.30 ppm in the 1 H NMR spectrum.…”

Section: Resultssupporting

confidence: 74%

Intramolecular N−H···H−Ru Proton−Hydride Interaction in Ruthenium Complexes with (2-(Dimethylamino)ethyl)cyclopentadienyl and (3-(Dimethylamino)propyl)cyclopentadienyl Ligands. Hydrogenation of CO₂to Formic Acid via the N−H···H−Ru Hydrogen-Bonded Complexes

et al. 1998

View full text Add to dashboard Cite

Addition of 1 equiv of HBF4 to (η5-C5H4(CH2) n NMe2)RuH(dppm) (n = 2, 3) gave [(η5-C5H4(CH2) n NMe2H+)RuH(dppm)]BF4, in which the amine function was protonated. Relaxation time T 1 measurements indicated the existence of an intramolecular N−H···H−Ru hydrogen-bonding interaction in these complexes. A spin saturation transfer study and H/D exchange experiment with [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BF4 revealed fast exchange, probably via a dihydrogen complex intermediate, between the hydride ligand and N−H. An attempt to grow single crystals of [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BPh4 for X-ray study resulted in isolation of crystals of the complex, [(η5:η1-C5H4(CH2)3NMe2)Ru(dppm)]BPh4, with the chelating (3-(dimethylamino)propyl)cyclopentadienyl ligand. Exposure of [(η5:η1-C5H4(CH2)3NMe2)Ru(dppm)]BF4 to 60 atm of H2 at 60 °C gave [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BF4 within 30 min. Reacting [(η5:η1-C5H4(CH2)3NMe2)Ru(dppm)]BAr‘4 (Ar‘ = 3,5-(CF3)2C6H3) with Ph2SiH2 yielded [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BAr‘4; it is proposed that hydrolysis of the η2-silane intermediate by adventitious moisture in the solvent affords an η2-dihydrogen species, and heterolytic cleavage of the dihydrogen ligand by the pendant amino group gives the final product. Heating solutions of [(η5:η1-C5H4(CH2) n NMe2)Ru(dppm)]BF4 under H2/CO2 (40 atm/40 atm) at 80 °C for 16 h gave formic acid in low yields (n = 2, TON = 6; n = 3, TON = 8). The formation of formic acid is best explained by a mechanism involving intramolecular heterolytic cleavage of the bound H2 to generate [(η5-C5H4(CH2) n NMe2H+)RuH(dppm)]BF4, followed by CO2 insertion into the Ru−H and then N−H protonation of the formato ligand. Carbon disulfide inserted into the Ru−H bond of [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BF4 to give [(η5-C5H4(CH2)3NMe2H+)Ru(η1-SCSH)(dppm)]BF4.

show abstract

Section: Resultssupporting

confidence: 74%

Intramolecular N−H···H−Ru Proton−Hydride Interaction in Ruthenium Complexes with (2-(Dimethylamino)ethyl)cyclopentadienyl and (3-(Dimethylamino)propyl)cyclopentadienyl Ligands. Hydrogenation of CO₂to Formic Acid via the N−H···H−Ru Hydrogen-Bonded Complexes

et al. 1998

View full text Add to dashboard Cite

show abstract

“…Wang et al have reported intramolecular coordination for the [2- (dimethylamino)ethyl]cyclopentadienyl ligand in manganese,20a molybdenum 12,20b and rhenium 20c complexes. The nitrogen is also coordinated in several titanium and zirconium complexes .…”

Section: Resultsmentioning

confidence: 99%

Transition-Metal Derivatives of a Functionalized Cyclopentadienyl Ligand. 15. Synthesis and Structures of Amino Cyclopentadienyl Derivatives of Rhodium(I) and Rhodium(III) Including Water-Soluble Compounds

Philippopoulos¹,

Hadjiliadis²,

Hart³

et al. 1997

Inorg. Chem.

View full text Add to dashboard Cite

The synthesis of monometallic rhodium(III) and rhodium(I) derivatives of dialkylamino-functionalized cyclopentadienyl using the corresponding cyclopentadiene as starting material is facilitated by the presence of the basic amino group. This procedure affords the chloro salts of the substituted rhodicinium cation [(eta(5)-C(5)H(4)(CH(2))(2)NMe(2)H)(2)Rh(III)](3+) ([1][Cl](3)) from the reaction of the [2-(dimethylamino)ethyl]cyclopentadiene with Na(3)Rh(III)Cl(6). 12H(2)O. Similarly the cationic half-sandwich complexes [(eta(5)-C(5)H(4)(CH(2))(n)()NMe(2)H)Rh(I)(cod)](+) (n = 2, [2][Cl], n = 3, [5][Cl]) are obtained from the reaction of the corresponding dialkylamino cyclopentadiene with [RhCl(cod)](2). These types of cationic complexes, 1, 2, and 5, bear pendant ammonium groups. The most classical procedure, starting from the lithium or more efficiently from the sodium cyclopentadienide salt, was used to synthesize neutral complexes [(eta(5)-C(5)H(4)(CH(2))(n)()NMe(2))Rh(I)(cod)] (n = 2, 3; n = 3, 4). The structure of the chloride bis(hexafluorophosphate) salt, [(eta(5)-C(5)H(4)(CH(2))(2)NMe(2)H)(2)Rh(III)](3+)(Cl(-))(PF(6)(-))(2), ([1][Cl][PF(6)](2)) was solved in the triclinic space group P&onemacr; with one molecule in the unit cell, the dimensions of which are a = 6.617(2) Å, b= 7.436(2) Å, c = 13.965(3) Å, alpha = 76.39(2) degrees, beta = 82.31(3) degrees, gamma = 87.26(2) degrees, and V = 661.8(3) Å(3). The noncentrosymmetric character of this solid is attributed to the chloride ion. The tetrafluoroborate salt [(eta(5)-C(5)H(4)(CH(2))(2)NMe(2)H)Rh(I)(cod)](+)(BF(4)(-)) ([2][BF(4)]) crystallizes in the tetragonal space group P4(2)/n with eight molecules in the unit cell, the dimensions of which are a= 21.183(2) Å, b = 21.179(3) Å, c= 8.324(2) Å, and V = 3734(1) Å(3). Least squares refinement leads to values for the conventional R index of [1][Cl][PF(6)](2) (0.0484 for 2191 reflections used) and of [2][BF(4)] (0.0525 for 1083 reflections used); in both cases I > 3sigma(I). As expected, compounds like [2][Cl](3,) [1][Cl][PF(6)](2), [2][Cl], [2][BF(4)], [5][Cl], and [5][BF(4)] are soluble in water.

show abstract

“…Allyl alcohol bound to the [CpRe(NO)(PPh 3 )] + fragment can undergo nucleophilic substitution at the hydroxyl group without affecting the alkene portion. − CpRe(NO)(CO)H inserts alkenes into its Re−H linkage to form the corresponding alkyl complexes . [Cp‘Re(NO)(PPh 3 )(CO)] + can also be made with a chiral-substituted Cp ring. − Furthermore, (η 5 ,η 1 -C 5 H 4 CH 2 CH 2 N Me 2 )Re(NO)(CO)Br has been prepared, and its chemistry is similar to that of CpRe(NO)(PPh 3 )X …”

Section: 22 Organometallic Complexesmentioning

confidence: 99%

Coordination and Organometallic Chemistry of Metal−NO Complexes

2002

View full text Add to dashboard Cite

Preparation and reactions of half-sandwich rhenium nitrosyl complexes containing a tethered amino ligand

Cited by 11 publications

References 24 publications

Intramolecular N−H···H−Ru Proton−Hydride Interaction in Ruthenium Complexes with (2-(Dimethylamino)ethyl)cyclopentadienyl and (3-(Dimethylamino)propyl)cyclopentadienyl Ligands. Hydrogenation of CO₂to Formic Acid via the N−H···H−Ru Hydrogen-Bonded Complexes

Intramolecular N−H···H−Ru Proton−Hydride Interaction in Ruthenium Complexes with (2-(Dimethylamino)ethyl)cyclopentadienyl and (3-(Dimethylamino)propyl)cyclopentadienyl Ligands. Hydrogenation of CO₂to Formic Acid via the N−H···H−Ru Hydrogen-Bonded Complexes

Transition-Metal Derivatives of a Functionalized Cyclopentadienyl Ligand. 15. Synthesis and Structures of Amino Cyclopentadienyl Derivatives of Rhodium(I) and Rhodium(III) Including Water-Soluble Compounds

Coordination and Organometallic Chemistry of Metal−NO Complexes

Contact Info

Product

Resources

About

Preparation and reactions of half-sandwich rhenium nitrosyl complexes containing a tethered amino ligand

Cited by 11 publications

References 24 publications

Intramolecular N−H···H−Ru Proton−Hydride Interaction in Ruthenium Complexes with (2-(Dimethylamino)ethyl)cyclopentadienyl and (3-(Dimethylamino)propyl)cyclopentadienyl Ligands. Hydrogenation of CO2to Formic Acid via the N−H···H−Ru Hydrogen-Bonded Complexes

Intramolecular N−H···H−Ru Proton−Hydride Interaction in Ruthenium Complexes with (2-(Dimethylamino)ethyl)cyclopentadienyl and (3-(Dimethylamino)propyl)cyclopentadienyl Ligands. Hydrogenation of CO2to Formic Acid via the N−H···H−Ru Hydrogen-Bonded Complexes

Transition-Metal Derivatives of a Functionalized Cyclopentadienyl Ligand. 15. Synthesis and Structures of Amino Cyclopentadienyl Derivatives of Rhodium(I) and Rhodium(III) Including Water-Soluble Compounds

Coordination and Organometallic Chemistry of Metal−NO Complexes

Contact Info

Product

Resources

About

Intramolecular N−H···H−Ru Proton−Hydride Interaction in Ruthenium Complexes with (2-(Dimethylamino)ethyl)cyclopentadienyl and (3-(Dimethylamino)propyl)cyclopentadienyl Ligands. Hydrogenation of CO₂to Formic Acid via the N−H···H−Ru Hydrogen-Bonded Complexes

Intramolecular N−H···H−Ru Proton−Hydride Interaction in Ruthenium Complexes with (2-(Dimethylamino)ethyl)cyclopentadienyl and (3-(Dimethylamino)propyl)cyclopentadienyl Ligands. Hydrogenation of CO₂to Formic Acid via the N−H···H−Ru Hydrogen-Bonded Complexes