An efficient method for the preparation of the first hybrid scorpionate/cyclopentadienyllithium compound as a new class of tridentate ligand is described. This compound is an excellent reagent for the introduction of this ligand into transition metal complexes.

The formation of CH(3) in the 248 or 266 nm photolysis of acetone (CH(3)C(O)CH(3)), 2-butanone (methylethylketone, MEK, CH(3)C(O)C(2)H(5)) and acetyl bromide (CH(3)C(O)Br) was examined using the pulsed photolytic generation of the radical and its detection by transient absorption spectroscopy at 216.4 nm. Experiments were carried out at room temperature (298 +/- 3 K) and at pressures between approximately 5 and 1500 Torr N(2). Quantum yields for CH(3) formation were derived relative to CH(3)I photolysis at the same wavelength in back-to-back experiments. For acetone at 248 nm, the yield of CH(3) was greater than unity at low pressures (1.42 +/- 0.15 extrapolated to zero pressure) confirming that a substantial fraction of the CH(3)CO co-product can dissociate to CH(3) + CO under these conditions. At pressures close to atmospheric the quantum yield approached unity, indicative of almost complete collisional relaxation of the CH(3)CO radical. Measurements of increasing CH(3)CO yield with pressure confirmed this. Contrasting results were obtained at 266 nm, where the yields of CH(3) (and CH(3)CO) were close to unity (0.93 +/- 0.1) and independent of pressure, strongly suggesting that nascent CH(3)CO is insufficiently activated to decompose on the time scales of these experiments at 298 K. In the 248 nm photolysis of CH(3)C(O)Br, CH(3) was observed with a pressure independent quantum yield of 0.92 +/- 0.1 and CH(3)CO remained below the detection limit, suggesting that CH(3)CO generated from CH(3)COBr photolysis at 248 nm is too highly activated to be quenched by collision. Similar to CH(3)C(O)CH(3), the photolysis of CH(3)C(O)C(2)H(5) at 248 nm revealed pressure dependent yields of CH(3), decreasing from 0.45 at zero pressure to 0.19 at pressures greater than 1000 Torr with a concomitant increase in the CH(3)CO yield. As part of this study, the absorption cross section of CH(3) at 216.4 nm (instrumental resolution of 0.5 nm) was measured to be (4.27 +/- 0.2) x 10(-17) cm(2) molecule(-1) and that of C(2)H(5) at 222 nm was (2.5 +/- 0.6) x 10(-18) cm(2) molecule(-1). An absorption spectrum of gas-phase CH(3)C(O)Br (210-305 nm) is also reported for the first time.

The preparation of new "scorpionate" ligands in the form of the lithium derivatives [(Li(bdmpzdta)(H(2)O))(4)] (1) [bdmpzdta = bis(3,5-dimethylpyrazol-1-yl)dithioacetate], [Li(bdphpza)(H(2)O)(THF)] (2) [bdphpza = bis(3,5-diphenylpyrazol-1-yl)acetate], and [Li(bdphpzdta)(H(2)O)(THF)] (3) [bdphpzdta = bis(3,5-diphenylpyrazol-1-yl)dithioacetate] has been carried out. Furthermore, a series of titanium complexes has been prepared by reaction of TiCl(4)(THF)(2) with the lithium reagents [(Li(bdmpza)(H(2)O))(4)] (4) [bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate] and 1. Under the appropriate experimental conditions neutral complexes, namely [TiCl(3)(kappa(3)-bdmpza)] (5), [TiCl(3)(kappa(3)-bdmpzdta)] (6), and [TiCl(2)(kappa(2)-bdmpzdta)(2)] (7), and cationic complexes, namely [TiCl(2)(THF)(kappa(3)-bdmpza)]Cl (8) and [TiCl(2)(THF)(kappa(3)-bdmpzdta)]Cl (9), were isolated. Complexes 8 and 9 undergo an interesting nucleophilic THF ring-opening reaction to give the corresponding alkoxide-containing species [TiCl(2)(kappa(3)-bdmpza)(O(CH(2))(4)Cl)] (10) and [TiCl(2)(kappa(3)-bdmpzdta)(O(CH(2))(4)Cl)] (11). A family of alkoxide-containing complexes of general formulas [TiCl(2)(kappa(3)-bdmpza)(OR)] [R = Me (12); R = Et (14); R = (i)Pr (16); R = (t)Bu (18)] and [TiCl(2)(kappa(3)-bdmpzdta)(OR)] [R = Me (13); R = Et (15); R = (i)Pr (17)] was also prepared. The structures of these complexes have been determined by spectroscopic methods, and in addition, the X-ray crystal structures of 3, 7, 10, and 11 were also established.

Pulsed laser photolysis combined with transient absorption spectroscopy and resonance fluorescence was used to examine the photolysis of OIO at a number of wavelengths corresponding to absorption bands in its visible spectrum between approximately 530 and 570 nm. Photolysis at 532 nm was found to result in substantial depopulation of the absorbing ground state, enabling an estimate for the absorption cross section of OIO at 610.2 nm of (6 +/- 2) x 10(-18) cm2 molecule(-1) to be obtained. No evidence was found for I atom formation following photolysis of OIO at 532, 562.3, 567.9 and 573.8 nm, enabling an upper limit to the I atom quantum yield of < 0.05 (560-580 nm) and < 0.24 (532 nm) to be established.