Vibrational Spectra of Nitrosyl-Substituted Transition-Metal Hydride Complexes: An Experimental and Theoretical Study of Carbonyldihydronitrosyl(trimethylphosphine)rhenium ([Re(CO)H2(NO)(PMe3)2])

Jacobsen, Heiko; Jonas, Volker; Werner, David; Messmer, Andreas; Panitz, Jan‐Christoph; Berke, Heinz; Thiel, Walter

doi:10.1002/(sici)1522-2675(19990210)82:2<297::aid-hlca297>3.0.co;2-y

HCA

1999

DOI: 10.1002/(sici)1522-2675(19990210)82:2<297::aid-hlca297>3.0.co;2-y

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Vibrational Spectra of Nitrosyl-Substituted Transition-Metal Hydride Complexes: An Experimental and Theoretical Study of Carbonyldihydronitrosyl(trimethylphosphine)rhenium ([Re(CO)H2(NO)(PMe3)2])

Heiko Jacobsen¹,

Volker Jonas²,

David Werner³

et al.

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Cited by 9 publications

References 14 publications

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Facile Synthetic Access to Rhenium(II) Complexes: Activation of Carbon–Bromine Bonds by Single‐Electron Transfer

Jiang¹,

Blacque²,

Fox³

et al. 2010

Chemistry A European J

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The five-coordinated Re(I) hydride complexes [Re(Br)(H)(NO)(PR(3))(2)] (R=Cy 1 a, iPr 1 b) were reacted with benzylbromide, thereby affording the 17-electron mononuclear Re(II) hydride complexes [Re(Br)(2)(H)(NO)(PR(3))(2)] (R=Cy 3 a, iPr 3 b), which were characterized by EPR, cyclic voltammetry, and magnetic susceptibility measurements. In the case of dibromomethane or bromoform, the reaction of 1 afforded Re(II) hydrides 3 in addition to Re(I) carbene hydrides [Re(=CHR(1))(Br)(H)(NO)(PR(3))(2)] (R(1)=H 4, Br 5; R=Cy a, iPr b) in which the hydride ligand is positioned cis to the carbene ligand. For comparison, the dihydrogen Re(I) dibromide complexes [Re(Br)(2)(NO)(PR(3))(2)(eta(2)-H(2))] (R=Cy 2 a, iPr 2 b) were reacted with allyl- or benzylbromide, thereby affording the monophosphine Re(II) complex salts [R(3)PCH(2)R'][Re(Br)(4)(NO)(PR(3))] (R'=-CH=CH(2) 6, Ph 7). The reduction of Re(II) complexes has also been examined. Complex 3 a or 3 b can be reduced by zinc to afford 1 a or 1 b in high yield. Under catalytic conditions, this reaction enables homocoupling of benzylbromide (turnover frequency (TOF): 3 a 150, 3 b 134 h(-1)) or allylbromide (TOF: 3 a 575, 3 b 562 h(-1)). The reaction of 6 a and 6 b with zinc in acetonitrile affords in good yields the monophosphine Re(I) complexes [Re(Br)(2)(NO)(MeCN)(2)(PR(3))] (R=Cy 8 a, iPr 8 b), which showed high catalytic activity toward highly selective dehydrogenative silylation of styrenes (maximum TOF of 61 h(-1)). Single-electron transfer (SET) mechanisms were proposed for all these transformations. The molecular structures of 3 a, 6 a, 6 b, 7 a, 7 b, and 8 a were established by single-crystal X-ray diffraction studies.

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Facile Synthetic Access to Rhenium(II) Complexes: Activation of Carbon–Bromine Bonds by Single‐Electron Transfer

Jiang¹,

Blacque²,

Fox³

et al. 2010

Chemistry A European J

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Hydrogen and dihydrogen bonding of transition metal hydrides

Jacobsen¹

2008

Chemical Physics

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Tuning photophysical properties with ancillary ligands in Ru(II) mono-diimine complexes

Sharmin¹,

Darlington²,

Hardcastle³

et al. 2009

Journal of Organometallic Chemistry

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The series of complexes [XRu(CO)(L–L)(L′)2][PF6] (X = H, TFA, Cl; L–L = 2,2′-bipyridyl, 1,10-phenanthroline, 5-amino-1,10-phenanthroline and 4,4′-dicarboxylic-2,2′-bipyridyl; L′2 = 2PPh3, Ph2 PC2H4PPh2, Ph2PCH═CHPPh2) have been synthesized from the starting complex K[Ru(CO)3(TFA)3] (TFA = CF3CO2) by first reacting with the phosphine ligand, followed by reaction with the L–L and anion exchange with NaPF6. In the case of L–L = phenanthroline and L′2 = 2PPh3, the neutral complex Ru(Ph3P)(CO)(1,10-phenanthroline)( TFA)2 is also obtained and its solid state structure is reported. Solid state structures are also reported for the cationic complexes where L–L = phenanthroline, L2 = 2PPh3 and X = Cl and for L–L = 2,2′-bipyridyl, L2 = 2PPh3 and X = H. All the complexes were characterized in solution by a combination of 1H and 31P NMR, IR, mass spectrometry and elemental analyses. The purpose of the project was to synthesize a series of complexes that exhibit a range of excited-state lifetimes and that have large Stokes shifts, high quantum yields and high intrinsic polarizations associated with their metal-to-ligand charge-transfer (MLCT) emissions. To a large degree these goals have been realized in that excited-state lifetimes in the range of 100 ns to over 1 μs are observed. The lifetimes are sensitive to both solvent and the presence of oxygen. The measured quantum yields and intrinsic anisotropies are higher than for previously reported Ru(II) complexes. Interestingly, the neutral complex with one phosphine ligand shows no MLCT emission. Under the conditions of synthesis some of the initially formed complexes with X = TFA are converted to the corresponding hydrides or in the presence of chlorinated solvents to the corresponding chlorides, testifying to the lability of the TFA Ligand. The compounds show multiple reduction potentials which are chemically and electrochemically reversible in a few cases as examined by cyclic voltammetry. The relationships between the observed photophysical properties of the complexes and the nature of the ligands on the Ru(II) is discussed.

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Vibrational Spectra of Nitrosyl-Substituted Transition-Metal Hydride Complexes: An Experimental and Theoretical Study of Carbonyldihydronitrosyl(trimethylphosphine)rhenium ([Re(CO)H2(NO)(PMe3)2])

Cited by 9 publications

References 14 publications

Facile Synthetic Access to Rhenium(II) Complexes: Activation of Carbon–Bromine Bonds by Single‐Electron Transfer

Facile Synthetic Access to Rhenium(II) Complexes: Activation of Carbon–Bromine Bonds by Single‐Electron Transfer

Hydrogen and dihydrogen bonding of transition metal hydrides

Tuning photophysical properties with ancillary ligands in Ru(II) mono-diimine complexes

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