Tetrazolyl and tetrazolylidene complexes of gold: A synthetic and structural study
dc.contributor.author | Gabrielli W.F. | |
dc.contributor.author | Nogai S.D. | |
dc.contributor.author | McKenzie J.M. | |
dc.contributor.author | Cronje S. | |
dc.contributor.author | Raubenheimer H.G. | |
dc.contributor.author | Gabrielli W.F. | |
dc.contributor.author | Nogai S.D. | |
dc.contributor.author | McKenzie J.M. | |
dc.contributor.author | Cronje S. | |
dc.contributor.author | Raubenheimer H.G. | |
dc.date.accessioned | 2011-05-15T16:05:14Z | |
dc.date.accessioned | 2011-05-15T16:05:14Z | |
dc.date.available | 2011-05-15T16:05:14Z | |
dc.date.available | 2011-05-15T16:05:14Z | |
dc.date.issued | 2009 | |
dc.date.issued | 2009 | |
dc.description.abstract | Lithiation of 1-benzyl-1H-tetrazole followed by transmetallation with [AuCl(PPh3)], [Au(C6F5)(tht)] or [AuCl(tht)] (tht = tetrahydrothiophene) and subsequent alkylation afforded cationic 1-benzyl-4-methyl-4,5-dihydro-1H-1,2,3,4-tetrazol-5-ylidene(triphenylphosphine) gold(i), 1, neutral 1-benzyl-4-methyl-4,5-dihydro-1H-1,2,3,4-tetrazol-5- ylidene(pentafluorophenyl)gold(i), 2, and a cationic biscarbene complex, bis(1-benzyl-4-methyl-4,5-dihydro-1H-1,2,3,4-tetrazol-5-ylidene)gold(i), 3. The first complex underwent a homoleptic rearrangement in solution to form 3. Reaction of [Au(N3)PPh3] with the three isocyanides (CH3)2C6H3NC, tBuNC and CyNC, respectively, yielded the corresponding neutral tetrazolyl(phosphine) complexes of gold, [1-(2,6-dimethylphenyl)-1H-tetrazol-5-yl](triphenylphosphine) gold(i), 4, [1-(tert-butyl)-1H-tetrazol-5-yl](triphenylphosphine)gold(i), 6, and [1-(cyclohexyl)-1H-tetrazol-5-yl](triphenylphosphine)gold(i), 7. Alkylation of 4 with methyl triflate on N4 allowed isolation of the crystalline carbene complex 1-(2,6-dimethylphenyl)-4-methyl-4,5-dihydro-1H-1,2,3,4-tetrazol- 5-ylidene)(triphenylphosphine)gold(i), 5. Complex 7 was not isolable in pure form but converts by isocyanide substitution of triphenylphosphine into [1-cyclohexylisocyanide][1-(cyclohexyl)-1H-tetrazol-5-yl]gold(i), 8. From a product mixture of 7 and 8 the transformed molecules [(cyclohexylamino)(ethoxy) carbene](1-cyclohexyl-1H-tetrazol-5-yl)gold(i), 9, and [bis(cyclohexylamino) carbene](1-cyclohexyltetrazol-5-yl)gold(i), 10, co-crystallised spontaneously after a long time at -20 °C. © 2009 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique. | |
dc.description.abstract | Lithiation of 1-benzyl-1H-tetrazole followed by transmetallation with [AuCl(PPh3)], [Au(C6F5)(tht)] or [AuCl(tht)] (tht = tetrahydrothiophene) and subsequent alkylation afforded cationic 1-benzyl-4-methyl-4,5-dihydro-1H-1,2,3,4-tetrazol-5-ylidene(triphenylphosphine) gold(i), 1, neutral 1-benzyl-4-methyl-4,5-dihydro-1H-1,2,3,4-tetrazol-5- ylidene(pentafluorophenyl)gold(i), 2, and a cationic biscarbene complex, bis(1-benzyl-4-methyl-4,5-dihydro-1H-1,2,3,4-tetrazol-5-ylidene)gold(i), 3. The first complex underwent a homoleptic rearrangement in solution to form 3. Reaction of [Au(N3)PPh3] with the three isocyanides (CH3)2C6H3NC, tBuNC and CyNC, respectively, yielded the corresponding neutral tetrazolyl(phosphine) complexes of gold, [1-(2,6-dimethylphenyl)-1H-tetrazol-5-yl](triphenylphosphine) gold(i), 4, [1-(tert-butyl)-1H-tetrazol-5-yl](triphenylphosphine)gold(i), 6, and [1-(cyclohexyl)-1H-tetrazol-5-yl](triphenylphosphine)gold(i), 7. Alkylation of 4 with methyl triflate on N4 allowed isolation of the crystalline carbene complex 1-(2,6-dimethylphenyl)-4-methyl-4,5-dihydro-1H-1,2,3,4-tetrazol- 5-ylidene)(triphenylphosphine)gold(i), 5. Complex 7 was not isolable in pure form but converts by isocyanide substitution of triphenylphosphine into [1-cyclohexylisocyanide][1-(cyclohexyl)-1H-tetrazol-5-yl]gold(i), 8. From a product mixture of 7 and 8 the transformed molecules [(cyclohexylamino)(ethoxy) carbene](1-cyclohexyl-1H-tetrazol-5-yl)gold(i), 9, and [bis(cyclohexylamino) carbene](1-cyclohexyltetrazol-5-yl)gold(i), 10, co-crystallised spontaneously after a long time at -20 °C. © 2009 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique. | |
dc.description.version | Article | |
dc.description.version | Article | |
dc.identifier.citation | New Journal of Chemistry | |
dc.identifier.citation | 33 | |
dc.identifier.citation | 11 | |
dc.identifier.citation | New Journal of Chemistry | |
dc.identifier.citation | 33 | |
dc.identifier.citation | 11 | |
dc.identifier.issn | 11440546 | |
dc.identifier.issn | 11440546 | |
dc.identifier.other | 10.1039/b907022b | |
dc.identifier.other | 10.1039/b907022b | |
dc.identifier.uri | http://hdl.handle.net/10019.1/13037 | |
dc.identifier.uri | http://hdl.handle.net/10019.1/13037 | |
dc.subject | carbenoid; cyanide; gold complex; phosphine derivative; trifluoromethanesulfonic acid; unclassified drug; alkylation; article; chemical reaction kinetics; chemical structure; complex formation; crystallography; lithiation; nuclear magnetic resonance spectroscopy; priority journal | |
dc.subject | carbenoid | |
dc.subject | cyanide | |
dc.subject | gold complex | |
dc.subject | phosphine derivative | |
dc.subject | trifluoromethanesulfonic acid | |
dc.subject | unclassified drug | |
dc.subject | alkylation | |
dc.subject | article | |
dc.subject | chemical reaction kinetics | |
dc.subject | chemical structure | |
dc.subject | complex formation | |
dc.subject | crystallography | |
dc.subject | lithiation | |
dc.subject | nuclear magnetic resonance spectroscopy | |
dc.subject | priority journal | |
dc.title | Tetrazolyl and tetrazolylidene complexes of gold: A synthetic and structural study | |
dc.title | Tetrazolyl and tetrazolylidene complexes of gold: A synthetic and structural study | |
dc.type | Article | |
dc.type | Article |