Structural and spectroscopic characterization of 17- and 18-electron piano-stool complexes of chromium. Thermochemical analyses of weak Cr-H bonds.
The 17-electron radical CpCr(CO)(2)(IMe)(•) (IMe = 1,3-dimethylimidazol-2-ylidene) was synthesized by the reaction of IMe with [CpCr(CO)(3)](2), and characterized by single crystal X-ray diffraction and by electron paramagnetic resonance (EPR), IR, and variable temperature (1)H NMR spectroscopy. The metal-centered radical is monomeric under all conditions and exhibits Curie paramagnetic behavior in solution. An electrochemically reversible reduction to 18-electron CpCr(CO)(2)(IMe)(-) takes place at E(1/2) = -1.89(1) V vs Cp(2)Fe(+•/0) in MeCN, and was accomplished chemically with KC(8) in tetrahydrofuran (THF). The salts K(+)(18-crown-6)[CpCr(CO)(2)(IMe)](-)·½THF and K(+)[CpCr(CO)(2)(IMe)](-)·(3)/(4)THF were crystallographically characterized. Monomeric ion pairs are found in the former, whereas the latter has a polymeric structure because of a network of K···O((CO)) interactions. Protonation of K(+)(18-crown-6)[CpCr(CO)(2)(IMe)](-)·½THF gives the hydride CpCr(CO)(2)(IMe)H, which could not be isolated, but was characterized in solution; a pK(a) of 27.2(4) was determined in MeCN. A thermochemical analysis provides the Cr-H bond dissociation free energy (BDFE) for CpCr(CO)(2)(IMe)H in MeCN solution as 47.3(6) kcal mol(-1). This value is exceptionally low for a transition metal hydride, and implies that the reaction 2 [Cr-H] → 2 [Cr(•)] + H(2) is exergonic (ΔG = -9.0(8) kcal mol(-1)). This analysis explains the experimental observation that generated solutions of the hydride produce CpCr(CO)(2)(IMe)(•) (typically on the time scale of days). By contrast, CpCr(CO)(2)(PCy(3))H has a higher Cr-H BDFE (52.9(4) kcal mol(-1)), is more stable with respect to H(2) loss, and is isolable.
Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, USA.
Edwin F
EF
van der Eide
Monte L
ML
Helm
Eric D
ED
Walter
R Morris
RM
Bullock
D002857:Chromium / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D004583:Electrons; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013696:Temperature
D009942:Organometallic Compounds; D002857:Chromium