Trichloro monophenoxide complexes of titanium(IV)

Nielson, Alastair J.; Schwerdtfeger, Peter; Waters, Joyce M.

doi:10.1039/a908435e

Cited by 24 publications

(30 citation statements)

References 38 publications

(29 reference statements)

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“…The structure of 1 is essentially similar to that found for dimeric [TiCl 2 (OC 6 H 5 ) 2 ], [11] but is described now in terms of modern bonding concepts. Selected bond lengths and angles are given in [15] ]. Theoretical calculations on the model complex [TiCl 3 (OC 6 H 2 Me 3 -2,4,6)] show that the terminal phenoxo ligand oxygen atom acts essentially as a 1-σ, 2-π donor to titanium but that there is also some O(2p) donation to the phenyl ring C=C(π*) orbital.…”

Section: Synthetic Studiesmentioning

confidence: 99%

“…Theoretical calculations on the model complex [TiCl 3 (OC 6 H 2 Me 3 -2,4,6)] show that the terminal phenoxo ligand oxygen atom acts essentially as a 1-σ, 2-π donor to titanium but that there is also some O(2p) donation to the phenyl ring C=C(π*) orbital. [15] The TiϪO (2) …”

Section: Synthetic Studiesmentioning

confidence: 99%

“…108.01 (9) The Ti-Cl(1) and Ti-Cl(2) bond lengths in complex 1 [2.2186(11) [15] Assuming that O(2) in complex 1 makes a single π-donor interaction with the titanium atom then the overall (formal) electron count for the complex is 16 so an 18-electron count can be attained if Cl(2p) to Ti(3d) donation occurs.…”

Section: Synthetic Studiesmentioning

confidence: 99%

“…The 1 H NMR spectrum in C 6 D 6 shows a single resonance for the tert-butyl groups, a doublet for the meta-protons of the phenyl ring but a broadened resonance for the ortho-protons. In the 13 [15] ) and this may represent a small change in the O(2p)-C=C(π*) bonding system associated with the smaller need for tight O(2)p-to-Ti(1)d orbital donation on addition of the second phenoxide ligand which is a better π-bonder than Cl. [15] Scheme 1.…”

Section: Synthetic Studiesmentioning

confidence: 99%

“…For example, [TiCl 2 (OC 6 H 5 ) 2 ] has a dimeric structure in the solid state [11] and there is conflicting evidence for the structure in solution, [12,13] [TiCl 2 (OC 6 H 3 Me 2 -2,6) 2 ] has a monomeric solid-state structure, [9] ArNH 2 and tetrahydrofuran) which have been characterised only by analytical data and IR spectroscopy. [14] We have reported [15] a comprehensive systematic study of the mono-(phenoxo) complexes [TiCl 3 (OAr)] (Ar = unsubstituted or substituted phenyl group) which included aspects of best synthetic method, co-ordination expansion and theoretical modelling. We report here a similar investigation for complexes of the type [TiCl 2 (OAr) 2 ] where changes are made to the size of the ortho-substituents of the phenyl rings.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Structure, Coordination Expansion and Theoretical Modelling of Dichlorobis(phenoxo) Titanium(IV) Complexes

et al. 2005

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Thermalisation of TiCl4 and two equivalents of a phenol in toluene is found to be the best preparative method for quantitative yields of a variety of dichlorobis(phenoxo) complexes. [TiCl2(OC6H4CMe3‐4)2] (1) is monomeric in benzene, a phenoxo‐bridged dimer in the solid state and undergoes coordination expansion with 4,4'‐dimethyl‐2,2′‐bipyridine (dmbipy) to give [TiCl2(OC6H4CMe3‐4)2(dmbipy)] (2). Also monomeric are [TiCl2(OC6H2Me3‐2,4,6)2] (3) and [TiCl2(OC6H3iPr2‐2,6)2] (5) which expand their coordination with dmbipy to give [TiCl2(OC6H2Me3‐2,4,6)2(dmbipy)] (4) and [TiCl2(OC6H3iPr2‐2,6)2(dmbipy)] (6). In contrast [TiCl2(OC6H2{CMe3}2‐2,6‐Me‐4)2] (7) is only partially formed by the thermolysis reaction and does not coordinatively expand with dmbipy. [TiCl2(OC6H3Me2‐2,4)2] (8) is monomeric in benzene and reacts to form [TiCl2(OC6H3Me2‐2,4)2(dmbipy)] (9). [TiCl2(OC6H3{CMe3}2‐2,4)2] (10) forms along with the tri‐phenoxo complex [TiCl{OC6H3(CMe3)2‐2,4}3]. [TiCl2(OC6H3CMe3‐2‐Me‐6)2] (11) is monomeric in benzene and forms [TiCl2(OC6H3CMe3‐2‐Me‐6)2(dmbipy)] (12). 2‐Phenylphenol and 1‐napthol form [TiCl2(OC6H4Ph‐2)2] (13) and [TiCl2(OC10H9)2] (14) which are monomeric in benzene. DFT calculations give structural parameters for monomeric [TiCl2(OC6H5)2] (15) in good agreement with the X‐ray data for [TiCl2(OC6H3Me2‐2,6)2]. Each oxygen of the phenoxo ligand in 15 acts essentially as a 2π donor to titanium and there is substantial pπ(O)‐pπ*(C=C) backbonding with the phenyl ring, which is absent in [TiCl2(OCH3)2] (16). The global minimum for the dimer [(TiCl2{OC6H5}{μ‐OC6H5})2] is in almost perfect agreement with the crystal structure obtained for [(TiCl2{OC6H5}{μ‐OC6H5})2] or [(TiCl2{OC6H4CMe3‐4}{μ‐OC6H4CMe3‐4})2] (1). The dimerisation energy for 15 is–26.2 kJ·mol–1. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Section: Synthetic Studiesmentioning

confidence: 99%

Section: Synthetic Studiesmentioning

confidence: 99%