Synthesis and Structure of (Triphenylsilyl)imido Complexes of Titanium and Zirconium

Li, Yahong; Banerjee, Sanjukta; Odom, Aaron L.

doi:10.1021/om050179s

Cited by 37 publications

(30 citation statements)

References 27 publications

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“…The third pyridine ligand is disposed trans to the imido group. Bond lengths and angles are unexceptional and were found to be very similar to those observed in titanium [23,25] and vanadium [21] analogues; the titaniumnitrogen bond lengths of the imido fragment is 1.7110 (13) Functionalized organoimido complexes of titanium, that is complexes that contain additional functional groups on the imido moiety, are extremely rare. [23,30] Since we have easy access to various Ti-imido complexes from readily available amines, it was of interest to probe the tolerance of our synthetic procedure towards the presence of functional groups on the alkyl/arylamine backbone, and also to learn the stability of the resulting functionalized imido compounds.…”

Section: General Synthesis Of the Imido Complexes [Ti(=nr)-cl 2 (Nhmementioning

confidence: 83%

“…[10b,12d, 25,29] When dissolved in pyridine, bis-dimethylamine adducts 1 are instantly and generally quantitatively converted into tris-pyridine complexes [Ti(=NR)Cl 2 (Py) 3 ] (2). In a few cases, it has been reported that the substitution of NHMe 2 ligands by pyridine is difficult or produces mixed NHMe 2 -pyridine adducts.…”

Section: General Synthesis Of the Imido Complexes [Ti(=nr)-cl 2 (Nhmementioning

confidence: 99%

“…[6a,13d,17c, [23][24][25][26] Some of these imido-titanium complexes present potential activity in olefin polymerization, [6] alkyne hydroamination, [13] and have been used for the synthesis of TiN thin films, [17a-17c] which further justifies the quest for the cheapest and the most direct route for the preparation of such useful precursors. is prepared from TiCl 4 , tBuNH 2 , and pyridine.…”

Section: Introductionmentioning

confidence: 99%

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A General and Facile One‐Step Synthesis of Imido–Titanium(IV) Complexes: Application to the Synthesis of Compounds Containing Functionalized or Chiral Imido Ligands and Bimetallic Diimido Architectures

2006

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One‐pot reactions of Ti(NMe2)4 with a wide range of primary alkyl, aryl, and silylamines RNH2 in the presence of excess chlorotrimethylsilane produced the corresponding imido–titanium(IV) complexes [Ti(=NR)Cl2(NHMe2)2] (1a–j), in which R = tBu, 1‐adamantane, Ph3C, Ph3Si, Ph, 2,6‐iPr2–C6H3, 2,6‐Cl2–C6H3, 2,6‐Br2–4‐Me–C6H2, C6F5, and 3,5‐(F3C)2–C6H3. This general synthesis, which starts from commercially available reagents, represents a simple and direct route to imido complexes. Reaction of complexes 1 with pyridine afforded the six‐coordinate tris‐pyridine adducts [Ti(=NR)Cl2(Py)3] (2). Another advantage of this method is its tolerance to other functional groups; complexes that contain halides, ether, dialkylamino, cyano, ethynyl, olefin, and nitro substituents on the imido moiety have been prepared. The use of enantiomerically pure primary amines affords the first group of titanium complexes that contain chiral imido groups, and the use of diamines produces diimido complexes. Alternatively, CH3I has been used as an alkylating agent to generate titanium–imido complexes of the type [Ti(NR)I2(THF)2]2. All compounds were fully characterized by spectroscopic methods (IR, 1H NMR, 13C NMR) and elemental analysis. Some of the compounds were also analyzed by single‐crystal X‐ray diffraction studies. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Section: General Synthesis Of the Imido Complexes [Ti(=nr)-cl 2 (Nhmementioning

confidence: 83%

Section: General Synthesis Of the Imido Complexes [Ti(=nr)-cl 2 (Nhmementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A General and Facile One‐Step Synthesis of Imido–Titanium(IV) Complexes: Application to the Synthesis of Compounds Containing Functionalized or Chiral Imido Ligands and Bimetallic Diimido Architectures

2006

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“…The silane 21 itself was prepared from triphenylsilyl chloride and ammonia. 3 In the case of sulfonamide 27 , this conversion was accomplished without the use of solvent. Thus, the byproduct trimethylsilyl chloride can be distilled off directly and recovered in greater then 75% yield.…”

Section: Resultsmentioning

confidence: 99%

Preparation of sulfonamides from N-silylamines

Naredla

Klumpp

2013

Tetrahedron Letters

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Sulfonamides have been prepared in high yields by the reactions of N-silylamines with sulfonyl chlorides and fluorides. In a competition experiment, the sulfonyl chlorides were found to be far more reactive than sulfonyl fluorides. The chemistry may be used to prepare aliphatic, aromatic, tertiary, secondary, and primary sulfonamides. It may also be done in the absence of solvent and the byproduct trimethylsilyl chloride recovered in good yield. Primary sulfonamides were synthesized from the sulfonyl chloride with aminotriphenyl silane (Ph3SiNH2), a conversion demonstrated with the synthesis of the carbonic anhydrase inhibitor, acetazolamide.

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“…Each salt reveals a polydecker arrangement, best described as m,Z 1 :Z 4 , m,Z 2 :Z 3 and m,Z 2 :Z 2 for lithium, sodium and potassium, respectively. 87 Work with ZrNa systems has also been extended to the preparation of the novel organometallic sphere [{(Bu t C 5 H 4 )(Bu t C 5 H 3 )Zr(m-H)Na} 2 Á OEt 2 ] 2 through the sodium reduction of (Bu t C 5 H 4 ) 2 ZrCl 2 . Reaction of this with Bu t Li/tmeda has afforded the monolithiation of both rings, as evidenced by the crystal structure of the thf-solvate (Z 5 -C 5 H 4 Li)(Z 7 -C 7 H 6 Li)Cr Á 8thf.…”

Section: Cyclopentadienyl and Related Derivativesmentioning

confidence: 99%

Alkali/coinage metals—organolithium, organocuprate chemistry

Haywood¹,

Wheatley²

Organometallic Chemistry

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The first half of this review features alkali metal-containing organometallics. Sub-categorization is primarily according to the organic anion component and, cases of extreme interest notwithstanding, discussion is limited to compounds that contain at least one carbon-alkali metal interaction. Each section opens up with a summary of recent synthetic and mechanistic advances. The emphasis of the article is, however, structural and, thereafter, discussion is arranged according to the analytical method employed for the structural elucidation of organometallics; solid-state investigations are followed by solution and gas phase work in that order. The second half of this article is divided into three categories, each one focusing on a different coinage metal. As with the alkali metals, discussion centres on compounds that contain at least one carbon-metal interaction. For each of the three group 11 metals, a brief description of synthetic and mechanistic work is presented prior to the discussion of solid-state, solution and gas phase structural investigations. The article covers the 2005-2007 literature. The alkali metalsThe recent appearance of Science of Synthesis provides a series of excellent articles highlighting recent developments in organic synthesis using organoalkali metal reagents. Volume 8a deals with synthetic aspects of lithium chemistry, including the deployment of alkyl-and cycloalkyl-, alkenyl-, allenyl-, acetylido-, 1 benzyl-, 2 aryl-and hetaryllithium 3 substrates. Volume 8b focuses on the higher alkali metals and includes articles dedicated to the use of alkyl-, alkenyl-, allyl-, and arylsodiums 4 and organometallic compounds of K, 5 Rb and Cs. 6

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Synthesis and Structure of (Triphenylsilyl)imido Complexes of Titanium and Zirconium

Cited by 37 publications

References 27 publications

A General and Facile One‐Step Synthesis of Imido–Titanium(IV) Complexes: Application to the Synthesis of Compounds Containing Functionalized or Chiral Imido Ligands and Bimetallic Diimido Architectures

A General and Facile One‐Step Synthesis of Imido–Titanium(IV) Complexes: Application to the Synthesis of Compounds Containing Functionalized or Chiral Imido Ligands and Bimetallic Diimido Architectures

Preparation of sulfonamides from N-silylamines

Alkali/coinage metals—organolithium, organocuprate chemistry

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Synthesis and Structure of (Triphenylsilyl)imido Complexes of Titanium and Zirconium

Cited by 37 publications

References 27 publications

A General and Facile One‐Step Synthesis of Imido–Titanium(IV) Complexes: Application to the Synthesis of Compounds Containing Functionalized or Chiral Imido Ligands and Bimetallic Diimido Architectures

A General and Facile One‐Step Synthesis of Imido–Titanium(IV) Complexes: Application to the Synthesis of Compounds Containing Functionalized or Chiral Imido Ligands and Bimetallic Diimido Architectures

Preparation of sulfonamides from N-silylamines

Alkali/coinage metals&#8212;organolithium, organocuprate chemistry

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Alkali/coinage metals—organolithium, organocuprate chemistry