Reactivity of (.eta.7-cycloheptatrienyl)(.eta.5-cyclopentadienyl)M (M = titanium, niobium) toward dithioacetic acid: preparation and characterization of (.eta.5-C5H5)Ti(S2CCH3)3 and (.eta.5-C5H5)Nb(.eta.2-S2)(S2CCH3)2

Andras, Maria T.; Duraj, Stan A.

doi:10.1021/ic00065a013

Cited by 12 publications

(9 citation statements)

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“…identical, and are comparable to the average Ti-S distances reported for the Ti() species Ti(S 2 CNEt 2 ) 4 (2.564 Å),9 CpTi(S 2 CMe) 3 (2.603 Å),10 and CpTi(S 2 CNMe 2 ) 3 (2.611 Å) 11. Although[2,6-…”

supporting

confidence: 81%

Lithium, titanium and vanadium dithiocarboxylatesElectronic supplementary information (ESI) available: additional crystallographic details. See http://www.rsc.org/suppdata/dt/b2/b210691d/

2003

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supporting

confidence: 81%

Lithium, titanium and vanadium dithiocarboxylatesElectronic supplementary information (ESI) available: additional crystallographic details. See http://www.rsc.org/suppdata/dt/b2/b210691d/

2003

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“…As a result, these weakly interacting electrons in the d xy orbitals on each vanadium center give rise to the EPR signal. [12] and Ta-complexes [(Cp*Ta) 2 (μ-S){μ-C(H)S 3 -k 2 S : k 1 S',S''}{μ-SC(H)S-k 2 C : k 1 S''',S''''}] [14] and [(Cp*Ta) 2 (μ-S)(μ-S 2 CH 2 CHS 2 -k 2 S : k 1 S',S'')(μ-H)(μ-S 2 CH 2 k 1 S''',S'''')]. [17] On the other hand, the four equatorial sulfur atoms of 4 a and 4 b are not located in the same plane which is reflected in the average S eq À MÀ S eq bond angles (4 a: 86. planar geometry (90°).…”

Section: Reactivity Of [Cp*vcl 2 ] 3 (1) With [Hs(ch 2 ) 2 Sh]mentioning

confidence: 99%

“…In 1993, Duraj group reported the first group 4 thiolato complex [CpTi(S 2 CCH 3 ) 3 ] (D) having dithioacetate ligands. [12] This complex is an example of seven-coordinated distorted pentagonal bipyramidal species, in which the Ti atom coordinated to six sulfur atoms and one Cp ligand. In 1990, Tatsumi synthesized various bis-and tris-chelated dithiolato Nb(IV) and Ta(V) and tetrakis(arenethiolato) complexes of divalent transition metals.…”

Section: Introductionmentioning

confidence: 99%

Syntheses, Structures, and Electronic Properties of Mono‐ and Bimetallic Thiolato Complexes Containing Unusual Coordination Modes of Thiolato Ligands

et al. 2023

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Synthesis, bonding and chemistry of mono‐ and bimetallic complexes supported by chelating thiolato ligands have been established. Treatment of [Cp*VCl2]3 (1) with [LiBH4 ⋅ THF] followed by the addition of ethane‐1,2‐dithiol led to the formation of an EPR active bimetallic vanadium thiolato complex [(Cp*V){μ‐(SCH2CH2S)‐κ2S,S′)2{V(SCH2CH2S‐SH)}] (2). In complex 2, two ethane‐1,2‐dithiolato ligands are symmetrically coordinated to two vanadium atoms through μ‐S atoms. Interestingly, when similar reactions were carried out with heavier group 5 metal precursors, such as [Cp*NbCl4] (3 a), it afforded monometallic thiolato complex [Cp*Nb(SCH2CH2S)(SCH2CH2S−CH2S)] (4 a). On the other hand, the Ta‐analogue [Cp*TaCl4] (3 b) yielded thiolato species [Cp*Ta(SCH2CH2S)(SCH2CH2S−CH2S)] (4 b) and [Cp*Ta(SCH2CH2S) (SCH2CH2S−S)] (5). In complexes 4 a and 4 b, one ethane‐1,2‐dithiolato and one trithiolato ligand are coordinated to Nb and Ta centers, respectively. Whereas, in complex 5, one ethane‐1,2‐dithiolato and one 2‐disulfanylethanethiolato is coordinated to the Ta center. Moreover, the photolytic reaction of 5 with [Mo(CO)5 ⋅ THF] yielded heterobimetallic thiolato complex [(Cp*Ta){μ‐(SCH2CH2S)‐κ2S,S′}{μ‐(SCH2CH2S−CH2(CH3)S)κ2S′′ : κ1S‐′′′′ : κ1S′′′′′}{Mo(CO)3}] (6). All the complexes have been characterized by multinuclear NMR spectroscopy and single crystal X‐ray diffraction studies. Further, computational analyses were performed to provide an insight into the bonding of these complexes.

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“…218 Treatment of (η 7 -C 7 H 7 )Ti(η 5 -C 5 H 5 ) with dithioacetic acid, CH 3 CS 2 H, leads to loss of the cycloheptatrienyl to give (η 5 -C 5 H 5 )Ti(S 2 CCH 3 ) 3 . 219 and Cp(η 8 SiC≡CSiMe 3 ] revealed that BTMSA serves as a four-electron ligand to two equivalent (η 8 -C 8 H 8 )Ti units. The average C-C distance of 1.51Å in the acetylene ligand is close to that of a sp 3 carbon -carbon single bond, however, the high thermal stability and a large down-field chemical shift of the acetylenic carbon atoms (δ292.8 ppm) suggests unusually high π -back-bonding in the Ti -acetylene bond.…”

Section: Cyclopentadienyl-cycloheptatri Enyl Complexesmentioning

confidence: 99%

Titanium: Organometallic Chemistry

Mintz

2005

Encyclopedia of Inorganic and Bioinorganic Chemistry

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The majority of titanium organometallic chemistry involves complexes in which the titanium is in its highest oxidation state (+4) with cyclopentadienyl derivatives as ancillary ligands. However, considerable chemistry has also been developed for complexes with titanium in the +3 and +2 oxidation state, with lesser amounts of chemistry developed for titanium in lower oxidation states (+1, 0). Since the early 1980s, chemists have placed considerable emphasis on the fine‐tuning of the structure and reactivity of titanium organometallic complexes. Particular emphasis has been devoted to tailoring the structure and reactivity of bis(cyclopentadienyl)titanium derivatives by incorporating electron‐donating, electron‐withdrawing, sterically demanding, or chiral substituents on the cyclopentadienyl ring. Considerable effort has gone into preparing ansa‐metallocenes with a wide variety of bridging groups and substituents to fine‐tune the reactivity catalysts prepared from them. In a similar manner, considerable effort has gone into the development of constrained geometry complexes. Several types of chiral substituted cyclopentadienyl, annulated cyclopentadienyl, ansa ‐metallocenes, and constrained geometry complexes have been prepared and applied to olefin polymerization and organic synthesis. Additional efforts at modifying the structure and reactivity by focusing on varying the oxidation state or coordination geometry at the titanium center have expanded over the past decade.

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Reactivity of (.eta.7-cycloheptatrienyl)(.eta.5-cyclopentadienyl)M (M = titanium, niobium) toward dithioacetic acid: preparation and characterization of (.eta.5-C5H5)Ti(S2CCH3)3 and (.eta.5-C5H5)Nb(.eta.2-S2)(S2CCH3)2

Cited by 12 publications

References 0 publications

Lithium, titanium and vanadium dithiocarboxylatesElectronic supplementary information (ESI) available: additional crystallographic details. See http://www.rsc.org/suppdata/dt/b2/b210691d/

Lithium, titanium and vanadium dithiocarboxylatesElectronic supplementary information (ESI) available: additional crystallographic details. See http://www.rsc.org/suppdata/dt/b2/b210691d/

Syntheses, Structures, and Electronic Properties of Mono‐ and Bimetallic Thiolato Complexes Containing Unusual Coordination Modes of Thiolato Ligands

Titanium: Organometallic Chemistry

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