Cycloaddition reactions across the TiO bond of (tmtaa)TiO (tmtaa = dianion of 7,16-dihydro-6,8,15,17-tetramethyldibenzo[b, i][1,4,8,11]tetraazacyclotetradecine)

Housmekerides, Chris E.; Pilato, Robert S.; Geoffroy, Gregory L.; Rheingold, Arnold L.

doi:10.1039/c39910000563

Cited by 24 publications

(6 citation statements)

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“…The molecular structure of 4·H 2 O displays an almost planar SnO 2 S core with a coordination of the sulfite moiety as a terminal ligand in a chelating fashion. This binding mode of the sulfite is unknown for main group metal compounds, and to our knowledge there are few examples with a terminally bonded sulfite group reported up to now for transition metals . Structurally characterized organometallic sulfites usually possess the sulfite entity in a bridging position to provide polymeric structures …”

Section: Resultsmentioning

confidence: 99%

Intramolecularly Coordinated Group 14 and 15 Chalcogenites

et al. 2013

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The synthesis of N→M intramolecularly coordinated group 14 and 15 chalcogenites is reported. The N→Sn intramolecularly coordinated organotin(IV) carbonate L(Ph)SnCO3 (1), where L is the N,C,N-chelating ligand 2,6-(Me2NCH2)2C6H3 –, reacts with SO2 and SeO2 to provide the organotin(IV) sulfite L(Ph)SnSO3 (4) and selenite [L(Ph)SnSeO3]2 (5), respectively. Treatment of [LSbO]2 (2) and [LBiO]2 (3) with SeO2 provided the organoantimony and bismuth selenites LSbSeO3 (6) and [LBiSeO3]3 (7), respectively. Compounds 5–7 are rare examples of mixed element oxides with well-defined stoichiometry MSeO3 (M = Sn, Sb, Bi). Compounds 4–7 were characterized by means of elemental analyses, 1H, 13C, 77Se, and 119Sn NMR spectroscopies, IR spectroscopy, and single-crystal X-ray diffraction analysis.

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Section: Resultsmentioning

confidence: 99%

Intramolecularly Coordinated Group 14 and 15 Chalcogenites

et al. 2013

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“…Complex 1 instantly reacts with 2 equiv of acetyl chloride to form [tmtaa]TiCl2 and acetic anhydride ( NMR: 2.18) (eq 1). This reaction likely proceeds [tmtaa]Ti(n2[0,5]-OSP(=S)(C6H4OMe)) (34) Ti(l)-N(l-*4) plane 1 0.74(2)" Ti(2)-N(5-8) plane : 0.752(9)" Ti(l)-N(l) 2.002(12) Ti(2)-N(5) 1.980(12) Ti(l)-N(2) 2.003 ( 14) Ti(2)-N(6) 1.991 (15) Ti(l)-N(3) 1.988 (13) Ti(2)-N(7) 2.023 (13) Ti( 1)-N(4)…”

Section: Resultsmentioning

confidence: 99%

Addition and cycloaddition reactions of the nucleophilic oxo and sulfido complexes [tmtaa]Ti:X (X = O, S; tmtaa = dianion of 7,16-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine)

Housmekerides¹,

Ramage²,

Kretz³

et al. 1992

Inorg. Chem.

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106

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“…When synthesizing complexes 1 and 2, the Ti=OǞCr binuclear complex is the major product. However, small amounts of the [Ti=OǞCrǟO=Ti]Cl trinuclear complex and homocoupled [(tmtaa)Ti=O], [Ti-O-Ti]Cl 2 , [16] are also observed. These side-products are much less soluble than the binuclear complexes and are thus easily separated by filtration from the reaction mixture.…”

Section: Synthesis and Spectroscopic Characterizationmentioning

confidence: 99%

Mono‐Oxido‐Bridged Heterobimetallic and Heterotrimetallic Compounds Containing Titanium(IV) and Chromium(III)

Huang

Weare

et al. 2014

Eur J Inorg Chem

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A series of oxido-bridged heterobi-and heterotrimetallic complexes, [(tmtaa)Ti=OǞCr(Por)Cl] and [(tmtaa)Ti= OǞCr(Por)ǟO=Ti(tmtaa)] + (tmtaa = 7,16-dihydro-6,8,15,17tetramethyldibenzo[b,i] [1,4,8,11]tetraazacyclotetradecine; Por = 5,10,15,20-tetraarylporphyrin), have been synthesized. To the best of our knowledge, these complexes are the first structurally characterized examples to contain a Ti=OǞCr or Ti=OǞCrǟO=Ti structural motif. Crystal structures of representative heterobimetallic compounds, including the Ti=OǞCr binuclear complex 2 and two separate trimers, [Ti=OǞCrǟO=Ti]SbF 6 (10) and [Ti=OǞCrǟO=Ti]Cl (12), are reported. The bi-and trimetallic molecules have similar [a] 5662 structural parameters, including Ti-O, Cr-O, and Ti-O-Cr bond lengths and angles with a linear Ti=OǞCr geometry.Magnetic studies showed that a high-spin Cr III (S = 3/2) center is present in both the bi-and trinuclear molecules. The redox potentials for Cr IV/III (ΔE = 320 mV) and Por/Por ·-(ΔE = 260 mV) can be tuned by modifying the porphyrin ligand. By determining the thermodynamics and kinetics of the formation of these complexes by titration experiments and electrochemistry, it was found that the bi-and trimetallic species undergo isomerization in solution, allowing easy substitution of the apical chlorido ligand.obtain a further understanding of chromophores based on MMCT from chromium(III) to titanium(IV). [2c-2e] Goedken and co-workers reported a method for the synthesis of mono-oxido-bridged heterobimetallic complexes in which a titanium terminal oxido complex, [(tmtaa)Ti=O] (tmtaa = 7,16-dihydro-6,8,15,17-tetramethyldibenzo[b,i]-[1,4,8,11]tetraazacyclotetradecine), was used as a Lewis base to form coordination complexes with Lewis acidic metal centers such as Cr III salen and Cr III porphyrin. [5] However, the structural, spectroscopic, and electrochemical properties of these complexes have not yet been reported. Herein we report the synthesis and characterization of a series of heterobi-and heterotrimetallic Ti=OǞCr compounds, finding that the reactivity and physical properties of these systems are more complex than initially described. This is the first definitive report of heterobi-and heterotrimetallic complexes prepared by utilizing [(tmtaa)Ti=O]. By rigorously characterizing the complex behavior of these systems, we have been able to rationally control molecular properties such as electrochemical potential and absorptivity. [15] Results and Discussion Synthesis and Spectroscopic CharacterizationThe reaction between [(tmtaa)Ti=O] and [Cr(Por)Cl] can proceed to form either the bi-or trimetallic species de-Eur.

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Cycloaddition reactions across the TiO bond of (tmtaa)TiO (tmtaa = dianion of 7,16-dihydro-6,8,15,17-tetramethyldibenzo[b, i][1,4,8,11]tetraazacyclotetradecine)

Abstract: The complex (tmtaa)Ti=O undergoes [2 + 21 cycloaddition of the Ti=O bond across the C=O bond of ketones and [(C,MeS)Re(CO),(N0)l+, the S=O bonds of SO2 and SO3, the C=S bond of CS2, and ring opens epoxides and cyclic anhydrides to give metallacycles.

Cited by 24 publications

References 11 publications

Intramolecularly Coordinated Group 14 and 15 Chalcogenites

Intramolecularly Coordinated Group 14 and 15 Chalcogenites

Addition and cycloaddition reactions of the nucleophilic oxo and sulfido complexes [tmtaa]Ti:X (X = O, S; tmtaa = dianion of 7,16-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine)

Mono‐Oxido‐Bridged Heterobimetallic and Heterotrimetallic Compounds Containing Titanium(IV) and Chromium(III)

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