A quintuple bond in chemistry is an unusual type of chemical bond first reported in 2005 for a dichromium compound. Single bonds, double bonds, and triple bonds are commonplace in chemistry. Quadruple bonds are rarer but occur especially for Cr, Mo, W, and Re, e.g. [Mo2Cl8]4− and [Re2Cl8]2−. In a quintuple bond, ten electrons participate in bonding between the two metal centers, allocated as σ2π4δ4.
In some cases of high-order bonds between metal atoms, the metal-metal bonding is facilitated by ligands that link the two metal centers and reduce the interatomic distance. By contrast, the chromium dimer with quintuple bonding is stabilized by bulky terphenyl (2,6-[(2,6-diisopropyl)phenyl]phenyl) ligand. The species is stable up to 200 °C.[1][2] The chromium-chromium quintuple bond has been analyzed with multireference ab-initio and DFT methods,[3] which were also used to elucidate the role of the terphenyl ligand, in which the flanking aryls were shown to interact very weakly with the chromium atoms, causing only a small weakening of the quintuple bond.[4] A 2007 theoretical study identified two global minima for quintuple bonded RMMR compounds: a trans-bent molecular geometry and surprisingly another trans-bent geometry with the R substituent in a bridging position.[5]
In 2005, a quintuple bond was postulated to exist in the hypothetical uranium molecule U2 based on computational chemistry.[6][7] Diuranium compounds are rare, but do exist; for example, the U2Cl2−8 anion.
In 2007 the shortest ever metal to metal bond (180.28 pm) was reported to exist also in a compound containing a quintuple chromium-chromium bond.[8]
Dimolybdenum quintuple bonds
In 2009 a dimolybdenum compound with a quintuple bond was reported with a Mo-Mo bond length of 202 pm.[9] The compound was synthesised starting from potassium octachlorodimolybdate (already contains a Mo2 quadruple bond) and a lithium amidinate:
- K4Mo2Cl8 + Li[HC(N-2,6-i-Pr2C6H3)2] → Mo2(μ-Cl)[Cl2Li(OEt2)][μ-η2-HC(N-2,6-i-Pr2C6H3)2]2
followed by reduction with potassium graphite:
- Mo2(μ-Cl)[Cl2Li(OEt2)][μ-η2-HC(N-2,6-i-Pr2C6H3)2]2 + KC8 → Mo2[μ-η2-HC(N-2,6-i-Pr2C6H3)2]2
References
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Wikinews has related news: Delaware scientists create shortest ever metal to metal bond |
- ^ Quintuple Bond Makes Its Debut First stable molecule with fivefold metal-metal bonding is synthesized Steve Ritter Chemical & Engineering News 26 September 2005 Volume 83, Number 39
- ^ Synthesis of a Stable Compound with Fivefold Bonding Between Two Chromium(I) Centers Tailuan Nguyen, Andrew D. Sutton, Marcin Brynda, James C. Fettinger, Gary J. Long, and Philip P. Power Published online 22 September 2005; 10.1126/science.1116789 Support info
- ^ Quantum Chemical Study of the Quintuple Bond between Two Chromium Centers in [PhCrCrPh: trans-Bent versus Linear Geometry] Marcin Brynda, Laura Gagliardi, Per-Olof Widmark, Philip P. Power, Björn O. Roos Angewandte Chemie International Edition Published online 3 May 2006
- ^ Large Differences in Secondary Metal−Arene Interactions in the Transition-Metal Dimers ArMMAr (Ar = Terphenyl; M = Cr, Fe, or Co): Implications for Cr−Cr Quintuple Bonding Giovanni La Macchia, Laura Gagliardi, Philip P. Power, and Marcin Brynda J. Am. Chem. Soc. 2008 ASAP Article doi:10.1021/ja0771890
- ^ The Many Ways To Have a Quintuple Bond Gabriel Merino, Kelling J. Donald, Jason S. D’Acchioli, and Roald Hoffmann J. Am. Chem. Soc. 2007 ASAP Article doi:10.1021/ja075454b
- ^ Quantum chemical calculations show that the uranium molecule U2 has a quintuple bond Laura Gagliardi, Björn O. Roos Nature 433, 848-851 24 February 2005 Abstract
- ^ New look for chemical bonds Belle Dumé 23 February 2005 PhysicsWeb
- ^ The Shortest Metal-Metal Bond Yet: Molecular and Electronic Structure of a Dinuclear Chromium Diazadiene Complex Kevin A. Kreisel, Glenn P. A. Yap, Olga Dmitrenko, Clark R. Landis, and Klaus H. Theopold Web Release Date: 30 October 2007; (Communication) doi:10.1021/ja076356t
- ^ Journey from Mo-Mo Quadruple Bonds to Quintuple Bonds Yi-Chou Tsai, Hong-Zhang Chen, Chie-Chieh Chang, Jen-Shiang K. Yu, Gene-Hsiang Lee, Yu Wang, and Ting-Shen Kuo J. AM. CHEM. SOC. 2009, 131, 12534–12535 doi:10.1021/ja905035f
See also
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