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Charmant JP Haddow MF Mistry R Norman NC Orpen AG Pringle PG 《Dalton transactions (Cambridge, England : 2003)》2008,(11):1409-1411
Treatment of the diphosphines ortho-B10H10C(P(t)Bu2)C(PR2) (R = Et, Cy, Ph) with HCl gives the zwitterionic, nido-12-vertex species B10H10C(PH(t)Bu2)C(PClR2); these reactions are reversed by the addition of NEt3. 相似文献
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Adams CJ Bartlett IM Carlton S Connelly NG Harding DJ Hayward OD Orpen AG Patron E Ray CD Rieger PH 《Dalton transactions (Cambridge, England : 2003)》2007,(1):62-72
The d4 halide complexes [MX(CO)(eta-RC[triple bond, length as m-dash]CR)Tp'] {X=F, Cl, Br or I; R=Me or Ph; M=Mo or W; Tp'=hydrotris(3,5-dimethylpyrazolyl)borate} undergo one-electron oxidation to the d3 monocations [MX(CO)(eta-RC[triple bond, length as m-dash]CR)Tp']+, isolable for M=W, R=Me. X-Ray structural studies on the redox pairs [WX(CO)(eta-MeC[triple bond, length as m-dash]CMe)Tp']z (X=Cl and Br, z=0 and 1), the ESR spectra of the cations [WX(CO)(eta-RC[triple bond, length as m-dash]CR)Tp']+ (X=F, Cl, Br or I; R=Me or Ph), and DFT calculations on [WX(CO)(eta-MeC[triple bond, length as m-dash]CMe)Tp']z (X=F, Cl, Br and I; z=0 and 1) are consistent with electron removal from a HOMO (of the d4 complexes) which is pi-antibonding with respect to the W-X bond, pi-bonding with respect to the W-C(O) bond, and delta-bonding with respect to the W-Calkyne bonds. The dependence of both oxidation potential and nu(CO) for [MX(CO)(eta-RC[triple bond, length as m-dash]CR)Tp'] shows an inverse halide order which is consistent with an ionic component to the M-X bond; the small size of fluorine and its closeness to the metal centre leads to the highest energy HOMO and the lowest oxidation potential. In the cations [MX(CO)(eta-RC[triple bond, length as m-dash]CR)Tp']+ electronegativity effects become more important, leading to a conventional order for Cl, Br and I. However, high M-F pi-donation is still facilitated by the short M-F distance. 相似文献
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MA Freitas CL Hendrickson AG Marshall 《Rapid communications in mass spectrometry : RCM》1999,13(15):1639-1642
We present a novel approach for the determination of activation energy for the unimolecular dissociation of a large (>50 atoms) ion, based on measurement of the unimolecular dissociation rate constant as a function of continuous-wave CO(2) laser intensity. Following a short ( approximately 1 s) induction period, CO(2) laser irradiation produces an essentially blackbody internal energy distribution, whose 'temperature' varies inversely with laser intensity. The only currently available method for measuring such activation energies is blackbody infrared radiative dissociation (BIRD). Compared with BIRD, FRAGMENT: (a) eliminates the need to heat the surrounding ion trap and vacuum chamber to each of several temperatures (each requiring hours for temperature equilibration); (b) offers a three-fold wider range of effective blackbody temperature; and (c) extends the range of applications to include initially cold ions (e.g., gas-phase H/D exchange). Our FRAGMENT-determined activation energy for dissociation of protonated bradykinin, 1.2 +/- 0.1 eV, agrees within experimental error to the value, 1.3 +/- 0.1 eV, previously reported by Williams et al. from BIRD experiments. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
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Adams CJ Anderson KM Baber RA Connelly NG Kandiah M Orpen AG 《Dalton transactions (Cambridge, England : 2003)》2004,(20):3353-3359
The nominally square-planar coordination of the d(8) complexes [MClL(1)L(2)(p-XC(6)H(4)NNNHC(6)H(4)X-p)](M = Rh, L(1)= L(2)= CO, X = H, Me, Et or F; M = Ir, L(1)= L(2)= CO, X = Me; M = Pd or Pt, L(1)= Cl, L(2)= PPh(3), X = Me; M = Pd, L(1)L(2)=eta(3)-C(3)H(5), X = Me), with the triazene N-bonded via the imine group, is supplemented by an axial M...H-N interaction involving the terminal amino group. 相似文献
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Clarke ML Ellis D Mason KL Orpen AG Pringle PG Wingad RL Zaher DA Baker RT 《Dalton transactions (Cambridge, England : 2003)》2005,(7):1294-1300
The fluoroaryl phosphines P{C6H3(CF3)2-3,5}3 (La) and P(C6F5)3 (Lb) form the complexes trans-[MCl2(La)2] and trans-[MCl2(Lb)2](M = Pd or Pt) which have been isolated and fully characterised. 31P NMR studies of competition experiments show that the stability of trans-[PdCl2L2] is in the order L = Lb< La 相似文献