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Synthesis, structures, and reactions of titanium, scandium, and yttrium complexes of diamino-bis(phenolate) ligands: Monomeric, dimeric, neutral, cationic, and multiply bonded derivatives

Boyd, C. L., Toupance, T., Tyrrell, B. R., Ward, Benjamin David, Wilson, C. R., Cowley, A. R. and Mountford, P. 2005. Synthesis, structures, and reactions of titanium, scandium, and yttrium complexes of diamino-bis(phenolate) ligands: Monomeric, dimeric, neutral, cationic, and multiply bonded derivatives. Organometallics 24 (2) , pp. 309-330. 10.1021/om0493661

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Abstract

New groups 3 and 4 organometallic and coordination compounds supported by the tetradentate diamino-bis(phenolate) ligands O2tBuNN‘ and O2MeNN‘ are reported [H2O2RNN‘ = (2-C5H4N)CH2N(2-HO-3,5-C6H2R2)2 where R = tBu or Me] along with some comparative studies with the tridentate amino-bis(phenolate) ligand O2tBuN (H2O2tBuN = nPrN(2-HO-3,5-C6H2tBu2)2). Reaction of Na2O2tBuNN‘ with ScCl3 and pyridine in THF gave monomeric Sc(O2tBuNN‘)Cl(py) (2), whereas Na2O2MeNN‘ gave the dimeric phenoxy-bridged Sc2(O2MeNN‘)2Cl2 (3). Reaction of Na2O2tBuNN‘ and YCl3 in neat pyridine gave the chloride-bridged, seven-coordinate dimer Y2(O2tBuNN‘)2(μ-Cl)2(py)2 (4). Reaction of M(CH2SiMe3)3(THF)2 (M = Sc or Y) with H2O2tBuNN‘ afforded M(O2tBuNN‘)(CH2SiMe3)(THF). The one-pot reaction of ScCl3 with Na2O2RNN‘ (R = tBu or Me) and Li[PhC(NSiMe3)2] gave the fluxional benzamidinate derivatives Sc(O2RNN‘){PhC(NSiMe3)2}. Treatment of Ti(NMe2)4 with H2O2RNN‘ gave the corresponding Ti(O2RNN‘)(NMe2)2 (R = tBu (11) or Me); 11 in turn reacts with HS-4-C6H4Me to give Ti(O2tBuNN‘)(NMe2)(S-4-C6H4Me). One-pot reactions of TiCl4(THF)2 with MeLi (2 equiv) followed by H2O2RNN‘ affords Ti(O2RNN‘)Cl2 (R = tBu (9) or Me (10)), which are cleanly methylated with MeMgBr to yield the corresponding Ti(O2RNN‘)Me2 (R = tBu (14) or Me (15)). The terminal imidotitanium compounds Ti(O2tBuNN‘)(NR)(py) (R = tBu or 2,6-C6H3Me2) were formed from the respective Ti(NR)Cl2(py)3 reagents and Na2O2tBuNN‘, and these react with CO2 by imido group transfer to yield the μ-oxo dimer Ti2(O2tBuNN‘)2(μ-O)2 (18) and RNCO. The related five-coordinate compounds Ti(O2tBuN)(NR)(py) (R = tBu, 2,6-C6H3Me2 (20) or 2,6-C6H3iPr2 (21)) were prepared in an analogous manner. These do not give identifiable metal products with CO2. Treatment of the dimethyl compounds 14 or 15 with B(ArF)3 or [CPh3][B(ArF)4] (ArF = C6F5) gave the fluxional, dimeric phenoxy-bridged cations [Ti2(O2RNN‘)2Me2]2+, which show very sluggish 1-hexene polymerization behavior. The compounds 2, 3, 4, 11, 9, 10, 16, 18, 20, and 21 have been crystallographically characterized.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: American Chemical Society
ISSN: 0276-7333
Last Modified: 04 Jun 2017 02:08
URI: http://orca.cf.ac.uk/id/eprint/9716

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