@article {2108,
	title = {Photophysical, dynamic and redox behavior of tris(2,6-diisopropylphenyl) phosphine},
	journal = {New Journal of Chemistry},
	volume = {32},
	number = {2},
	year = {2008},
	note = {Times Cited: 8Boere, Rene T. Bond, Alan M. Cronin, Steve Duffy, Noel W. Hazendonk, Paul Masuda, Jason D. Pollard, Kyle Roemmele, Tracey L. Tran, Peter Zhang, Yuankui},
	pages = {214-231},
	abstract = {The title phosphine, Dipp(3)P, was synthesized using an aryl copper reagent and the structure determined by X-ray crystallography (R=2.94\%): d(P - C)=1.852(1) angstrom, angle C - P - C=111.88(5)degrees. In hexane solution, the electronic spectrum displays 3 bands [326 (9.3), 254 (8.7), 205 (11.4) nm (log|epsilon|)] and the fluorescence spectrum has a Stokes shift of 129 kJ mol(-1). NMR: ( d) P-31= - 49.7 ppm in solution and - 49.5 in the solid (CP-MAS). Room temperature 1 H and 13 C spectra reflect D-3 symmetry, changing below - 30 degrees C to C-3. A variable temperature NMR study provided an activation enthalpy of 49(+/- 1) kJ mol(-1) and entropy of 24 - 27(+/- 5) J mol(-1) K-1. An energy surface calculation using HF/3-21G theory discovered a single low-energy path describing pyramidal inversion through a transition state that is close to D3 geometry. The B3LYP/6-31G(d) calculated barrier to planarization is 37.5 kJ mol(-1). Voltammetric studies employing cyclic, rotating disk, steady state and Fourier Transform ac methods confirm a fully chemically reversible one-electron oxidation of Dipp(3)P to Dipp(3)P(+center dot) at +0.18 (CH3CN - (Bu4NPF6)-Bu-n) and +0.09 (CH2Cl2 - (Bu4NPF6)-Bu-n) V vs. Fc(+/0) (Fc=ferrocene). The diffusion coefficient for Dipp(3)P is 1.0 - 1.2 x 10(5) cm(2) s(-1). The electrode process displays quasi-reversible electron transfer kinetics [k(s)approximate to 0.01 (CH2Cl2) to 0.08 (CH3CN) cm s(-1)]. Optically transparent thin layer electrolysis reversibly generates Dipp(3)P(+center dot) in CH2Cl2 - (Bu4NPF6)-Bu-n [UV- Vis: 498 (3.31), 456 (3.29), 373 (4.04), 357 (3.84), 341 (3.49), 296 (3.78), 385 (3.91), 251 (3.99) nm (log|epsilon|)]. The EPR spectrum of Dipp(3)P(+center dot) in solution is a doublet (a(P)=23.9 mT, g=2.008), and in frozen solution is axial (a(parallel to)=42.6 mT, g(parallel to)=2.0045; a(perpendicular to)=12.7 mT, g(perpendicular to)=2.0085 mT).},
	isbn = {1144-0546},
	url = {<Go to ISI>://WOS:000253014300005},
	author = {Boer{\'e}, R. T. and Bond, A. M. and Cronin, S. and Duffy, N. W. and P. Hazendonk and Masuda, J. D. and Pollard, K. and Roemmele, T. L. and Tran, P. and Zhang, Y. K.}
}
