Crystal structure of tetraguanidinium tri(carbonato)oxotitanium(IV) dihydrate, [C(NH2)3]4[TiO(CO3)3]·2H2O

Li, Peng-Ju; Huang, Sijia; Huang, K.F.; Wang, Ru‐Ji; Mak, Thomas C. W.

doi:10.1016/s0020-1693(00)83203-x

Cited by 16 publications

(3 citation statements)

References 13 publications

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“…Structurally characterized examples of complexes containing terminal titanyl units are known and typically contain nitrogen-based macrocyclic ligands , such as porphyrins, phthalocyanines, and tacn derivatives (tacn = 1,4,7-triazacyclononane); , however, examples containing an oxygen-only coordination environment at titanium are extremely rare . Such examples include [OTi(OSMe 2 ) 5 ] 2+ and [OTi(CO 3 ) 3 ] 4– complexes and a sandwich-type 8-tungsto-2-arsenate(III) POM system ([(OTi) 2 (α-AsW 9 O 33 ) 2 ] 4– ) . Additionally, direct evidence for the formation of terminal [OTi(aq)] 2+ units in dilute acidic aqueous solutions of Ti(IV) has been observed .…”

Section: Resultsmentioning

confidence: 99%

Terminal Titanyl Complexes of Tri- and Tetrametaphosphate: Synthesis, Structures, and Reactivity with Hydrogen Peroxide

Stauber

Cummins

2017

Inorg. Chem.

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The synthesis and characterization of tri- and tetrametaphosphate titanium(IV) oxo and peroxo complexes is described. Addition of 0.5 equiv of [OTi(acac)] to dihydrogen tetrametaphosphate ([POH]) and monohydrogen trimetaphosphate ([POH]) provided a bis(μ,κ,κ) tetrametaphosphate titanyl dimer, [OTiPO] (1; 70% yield), and a trimetaphosphate titanyl acetylacetonate complex, [OTiPO(acac)] (2; 59% yield). Both 1 and 2 have been structurally characterized, crystallizing in the triclinic P1̅ and monoclinic P2 space groups, respectively. These complexes contain Ti≡O units with distances of 1.624(7) and 1.644(2) Å, respectively, and represent rare examples of structurally characterized terminal titanyls within an all-oxygen coordination environment. Complexes 1 and 2 react with hydrogen peroxide to produce the corresponding peroxotitanium(IV) metaphosphate complexes [OTiPO](3; 61% yield) and [OTiPO(acac)] (4; 65% yield), respectively. Both 3 and 4 have been characterized by single-crystal X-ray diffraction studies, and their solid-state structures are presented. Complex 3 functions as an oxygen atom transfer (OAT) reagent capable of oxidizing phosphorus(III) compounds (P(OMe), PPh) and SMe at ambient temperature to result in the corresponding organic oxide with regeneration of dimer 1.

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Section: Resultsmentioning

confidence: 99%

Terminal Titanyl Complexes of Tri- and Tetrametaphosphate: Synthesis, Structures, and Reactivity with Hydrogen Peroxide

Stauber

Cummins

2017

Inorg. Chem.

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“…Ti 4+ [ Fig. S1(j)] is the only example of this coordination polyhedron, in [C( (ICSD 66308;Li et al, 1990), bonding to six O 2À ions from CO 3 groups (0.30-0.46 v.u.) and making a partial double bond (1.50 v.u.)…”

Section: Mechanism (3)(ii): Ion Configurations Primarily Distorted VImentioning

confidence: 99%

Bond-length distributions for ions bonded to oxygen: results for the transition metals and quantification of the factors underlying bond-length variation in inorganic solids

Gagné

Hawthorne

2020

IUCrJ

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Bond-length distributions are examined for 63 transition metal ions bonded to O2− in 147 configurations, for 7522 coordination polyhedra and 41 488 bond distances, providing baseline statistical knowledge of bond lengths for transition metals bonded to O2−. A priori bond valences are calculated for 140 crystal structures containing 266 coordination polyhedra for 85 transition metal ion configurations with anomalous bond-length distributions. Two new indices, Δtopol and Δcryst, are proposed to quantify bond-length variation arising from bond-topological and crystallographic effects in extended solids. Bond-topological mechanisms of bond-length variation are (1) non-local bond-topological asymmetry and (2) multiple-bond formation; crystallographic mechanisms are (3) electronic effects (with an inherent focus on coupled electronic vibrational degeneracy in this work) and (4) crystal-structure effects. The indices Δtopol and Δcryst allow one to determine the primary cause(s) of bond-length variation for individual coordination polyhedra and ion configurations, quantify the distorting power of cations via electronic effects (by subtracting the bond-topological contribution to bond-length variation), set expectation limits regarding the extent to which functional properties linked to bond-length variation may be optimized in a given crystal structure (and inform how optimization may be achieved) and more. These indices further provide an equal footing for comparing bond-length variation and the distorting power of ions across ligand types, including resolution for heteroligand polyhedra. The observation of multiple bonds is found to be primarily driven by the bond-topological requirements of crystal structures in solids. However, sometimes multiple bonds are observed to form as a result of electronic effects (e.g. the pseudo Jahn–Teller effect, PJTE); resolution of the origins of multiple-bond formation follows calculation of the Δtopol and Δcryst indices on a structure-by-structure basis. Non-local bond-topological asymmetry is the most common cause of bond-length variation in transition metal oxides and oxysalts, followed closely by the PJTE. Non-local bond-topological asymmetry is further suggested to be the most widespread cause of bond-length variation in the solid state, with no a priori limitations with regard to ion identity. Overall, bond-length variations resulting from the PJTE are slightly larger than those resulting from non-local bond-topological asymmetry, comparable with those resulting from the strong JTE, and less than those induced by π-bond formation. From a comparison of a priori and observed bond valences for ∼150 coordination polyhedra in which the strong JTE or the PJTE is the main reason underlying bond-length variation, the JTE is found not to have a cooperative relation with the bond-topological requirements of crystal structures. The magnitude of bond-length variation caused by the PJTE decreases in the following order for octahedrally coordinated d 0 transition metal oxyanions: Os8+ > Mo6+ > W6+ >> V5+ > Nb5+ > Ti4+ > Ta5+ > Hf4+ > Zr4+ > Re7+ >> Y3+ > Sc3+. Such ranking varies by coordination number; for [4] it is Re7+ > Ti4+ > V5+ > W6+ > Mo6+ > Cr6+ > Os8+ >> Mn7+; for [5] it is Os8+ > Re7+ > Mo6+ > Ti4+ > W6+ > V5+ > Nb5+. It is concluded that non-octahedral coordinations of d 0 ion configurations are likely to occur with bond-length variations that are similar in magnitude to their octahedral counterparts. However, smaller bond-length variations are expected from the PJTE for non-d 0 transition metal oxyanions.

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“…The titanyl(IV) ion is only stable and soluble in aqueous solution as complexes with, e.g., sulfate, phosphate, oxalate, citrate, lactate, malate or tartrate ions [9]. The number of reported crystal structures with an isolated titanyl(IV) complex is very limited, including Ba 2 [TiO(Si 2 O 7 ) 2 ] [10], Sr 2 [TiO(PO 4 ) 2 ] [11] (C(NH 2 ) 3 ) 4 [TiO(CO 3 ) 3 ]·2H 2 O [12] and [TiO(OS(CH 3 ) 2 ) 5 ]Cl 2 [13, 14]. In Ba 2 [TiO(Si 2 O 7 ) 2 ] and [TiO(OS(CH 3 ) 2 ) 5 ]Cl 2 titanium(IV) binds strongly to an oxogroup at ca.…”

Section: Introductionmentioning

confidence: 99%

Structure of a Hydrated Sulfonatotitanyl(IV) Complex in Aqueous Solution and the Dimethylsulfoxide Solvated Titanyl(IV) Ion in Solution and Solid State

Lundberg

Persson

2017

J Solution Chem

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The coordination chemistry of oxotitanium(IV) or titanyl(IV), TiO2+, has been studied in solution by X-ray methods. The titanyl(IV) ion hydrolyzes easily in aqueous systems to solid titanium dioxide as long as it is not stabilized through complexation. In this study the structures of the hydrated bissulfatotitanyl(IV) complex and the dimethylsulfoxide (DMSO) solvated titanyl(IV) ions have been determined. In isolated monomeric titanyl complexes titanium(IV) binds strongly to a doubly bound oxo group at ca. 1.64 Å, to four ligands in the equatorial plane almost perpendicular to the Ti=O bond at ca. 2.02 Å, and there is one weakly bound ligand, trans to the Ti=O bond, at ca. 2.22 Å, for oxygen donor ligands; the O=Ti–Oeq bond angles are 95°–100°. The structure of the DMSO solvated titanyl(IV) ion in the solid state is maintained in DMSO solution.Electronic supplementary materialThe online version of this article (doi:10.1007/s10953-017-0581-3) contains supplementary material, which is available to authorized users.

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Crystal structure of tetraguanidinium tri(carbonato)oxotitanium(IV) dihydrate, [C(NH2)3]4[TiO(CO3)3]·2H2O

Cited by 16 publications

References 13 publications

Terminal Titanyl Complexes of Tri- and Tetrametaphosphate: Synthesis, Structures, and Reactivity with Hydrogen Peroxide

Terminal Titanyl Complexes of Tri- and Tetrametaphosphate: Synthesis, Structures, and Reactivity with Hydrogen Peroxide

Bond-length distributions for ions bonded to oxygen: results for the transition metals and quantification of the factors underlying bond-length variation in inorganic solids

Structure of a Hydrated Sulfonatotitanyl(IV) Complex in Aqueous Solution and the Dimethylsulfoxide Solvated Titanyl(IV) Ion in Solution and Solid State

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