Insertion of [Pt(PEt<sub>3</sub>)<sub>2</sub>] into a Strained Si−C Bond of Diphenylsila[1]molybdarenophane

Lund, Clinton L.; Bagh, Bidraha; Quail, J. Wilson; Müller, Jens

doi:10.1021/om100099f

Cited by 9 publications

(3 citation statements)

References 32 publications

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“…A mechanism for the reaction was proposed that involved OA of Me 3 SiCH 2 I to Pd, to form (I t Bu)Pd(CH 2 SiMe 3 )I (+ I t Bu), and the I t Bu carbene attacks the silicon center, ejecting iodide and initiating a sequence leading to the products. Insertion of [Pt(PEt 3 ) 2 ] into strained Si-C bonds has been speculated …”

Section: Oxidative Addition Reactions Of Lanthanides/actinides and Of...mentioning

confidence: 99%

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Reactions of Hydrosilanes with Transition Metal Complexes

2016

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This third review in a series involving reactions of hydrosilanes and transition metal complexes and characterization of the products covers the period 2009 thru 2013. After a brief discussion of other synthetic methods used for the formation of Si-TM complexes, Section 3 provides an extended discussion of the types of ligands and metal complexes used as reactants with hydrosilanes. The increase in use of pincer ligands in forming stable, isolable complexes is featured. Three tables list the complexes reported for primary, secondary, and tertiary silanes. Many reactions leading to SiTM complexes are initiated by loss of a ligand prior to oxidative addition of the hydrosilane or by a metathesis reaction. Structural data are tabulated for the isolated complexes and provide the Si-TM bond ranges for the elements in the "d" block. A major section on nonclassical (σ or agostic) complexes includes two general groupings with Si-H···TM and M-H···Si interactions. A section on solution processes identified by NMR spectroscopy is dominated by hydride exchange examples. A section on bonding outlines a unifying bonding description that has been proposed as well as calculations reported for Si-TM complexes, both real and hypothetical examples.

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Section: Oxidative Addition Reactions Of Lanthanides/actinides and Of...mentioning

confidence: 99%

“…Insertion of [Pt(PEt 3 ) 2 ] into strained Si-C bonds has been speculated. 295 In several reactions, a Me-substituent on Si was transferred to a metal center. 394,395 One example is shown in eq 98 (several other cases have been published).…”

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confidence: 98%

Reactions of Hydrosilanes with Transition Metal Complexes

2016

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“…The following report addresses this deficiency. In 2005, our research group published the first aluminum-bridged sandwich compound; since then, we expanded the family of aluminum- and gallium-bridged metallacyclophanes from ferrocenophanes to vanadarenophanes, chromarenophanes, molybdarenophanes, and ruthenocenophanes . For all these strained sandwich species, a salt metathesis between a dilithiated sandwich compound and a respective group 13 element dichloride RECl 2 had been employed, with R being a bulky, intramolecularly coordinating ligand (Chart ).…”

Section: Introductionmentioning

confidence: 99%

ansa-Zirconocenes with Aluminum or Gallium in Bridging Positions

Lund¹,

Hanson²,

Schatte

et al. 2010

Organometallics

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Bis(cyclopentadienyl)aluminum and -gallium species of the type (Pytsi)ECp2 [E = Al (2a), Ga (2b); Pytsi = C(SiMe3)2SiMe2(2-C5H4N)] have been prepared from NaCp and respective dichlorides (Pytsi)ECl2 in isolated yields of 65% (2a) and 83% (2b). In addition to applying standard methods of characterization (NMR spectroscopy, CHN analysis, and MS), the molecular structures of both compounds were solved by single-crystal X-ray crystallography. Reactions between 2a or 2b with Zr(NMe2)4 in benzene, followed by addition of an excess of ClSiMe3, gave the first ansa-zirconocene dichlorides with aluminum (4a) or gallium (4b) in bridging position. The gallium compound 4b was isolated in a yield of 40% and characterized by NMR spectroscopy, CHN analysis, and mass spectrometry. The aluminum species 4a could not be obtained in an analytically pure form; it was characterized by NMR spectroscopy, and its molecular structure was determined by single-crystal X-ray analysis. The angle between the two planes of the Cp ligands in 4a was found to be 57.17(11)°, which is larger than in Cp2ZrCl2 (α = 53.5°) and smaller than in silicon-bridged ansa-zirconocene dichlorides (e.g., Me2Si(C5H4)2ZrCl2: α = 60.1°). Crystallization attempts of 4a from DCCl3 solutions gave crystals of the new species (Pytsi)AlCl[(C5H4)ZrCp] (7), which was characterized by NMR spectroscopy and single-crystal X-ray analysis. In comparison to the Pytsi-containing species 2a and 2b, the less sterically protected compound [2-(Me2NCH2)C6H4]AlCp2 (6), which was prepared from NaCp and [2-(Me2NCH2)C6H4]AlCl2 in yields of 94% and characterized by standard methods (NMR, CHN, and MS), reacted with Zr(NMe2)4 to give the known Cp2Zr(NMe2)2. The targeted ansa-species was not formed, as judged by 1H NMR spectroscopy. The gallium-bridged compound 4b and Cp2ZrCl2, respectively, had been tested for polymerizations of ethylene utilizing MAO as an activator (300 equiv of MAO; 5 or 10 μmol of precatalyst; 15 or 70 psi), resulting in activities of 637 to 1080 for 4b and of 640 to 2601 kg PE (mol Zr)−1 h−1 atm−1 for Cp2ZrCl2.

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Synthesis and Reactivity of Boron‐, Silicon‐, and Tin‐Bridged ansa‐Cyclopentadienyl–Cycloheptatrienyl Titanium Complexes (Troticenophanes)

Braunschweig

Fuß

Mohapatra

et al. 2010

Chemistry A European J

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A novel one-pot method was developed for the preparation of [Ti(η(5)-C(5)H(5))(η(7)-C(7)H(7))] (troticene, 1) by reaction of sodium cyclopentadienide (NaCp) with [TiCl(4)(thf)(2)], followed by reduction of the intermediate [(η(5)-C(5)H(5))(2)TiCl(2)] with magnesium in the presence of cycloheptatriene (C(7)H(8)). The [n]troticenophanes 3 (n=1), 4, 8, 10 (n=2), and 11 (n=3) were synthesized by salt elimination reactions between dilithiated troticene, [Ti(η(5)-C(5)H(4)Li)(η(7)-C(7)H(6)Li)]⋅pmdta (2) (pmdta = N,N',N',N'',N''-pentamethyldiethylenetriamine), and the appropriate organoelement dichlorides Cl(2)Sn(Mes)(2) (Mes = 2,4,6-trimethylphenyl), Cl(2)Sn(2)(tBu)(4), Cl(2)B(2)(NMe(2))(2), Cl(2)Si(2)Me(4), and (ClSiMe(2))(2)CH(2), respectively. Their structural characterization was carried out by single-crystal X-ray diffraction and multinuclear NMR spectroscopy. The stanna[1]- and stanna[2]troticenophanes 3 and 4 represent the first heteroleptic sandwich complexes bearing Sn atoms in the ansa bridge. The reaction of 3 with [Pt(PEt(3))(3)] resulted in regioselective insertion of the [Pt(PEt(3))(2)] fragment into the Sn-C(ipso) bond between the tin atom and the seven-membered ring, which afforded the platinastanna[2]troticenophane 5. Oxidative addition was also observed upon treatment of 4 with elemental sulfur or selenium, to produce the [3]troticenophanes [Ti(η(5)-C(5)H(4)SntBu(2))(η(7)-C(7)H(6)SntBu(2))E] (6: E=S; 7: E=Se). The B-B bond of the bora[2]troticenophane 8 was readily cleaved by reaction with [Pt(PEt(3))(3)] to form the corresponding oxidative addition product [Ti(η(5)-C(5)H(4)BNMe(2))(η(7)-C(7)H(6)BNMe(2))Pt(PEt(3))(2)] (9). The solid-state structures of compounds 5, 6, and 9 were also determined by single-crystal X-ray diffraction.

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Insertion of [Pt(PEt₃)₂] into a Strained Si−C Bond of Diphenylsila[1]molybdarenophane

Cited by 9 publications

References 32 publications

Reactions of Hydrosilanes with Transition Metal Complexes

Reactions of Hydrosilanes with Transition Metal Complexes

ansa-Zirconocenes with Aluminum or Gallium in Bridging Positions

Synthesis and Reactivity of Boron‐, Silicon‐, and Tin‐Bridged ansa‐Cyclopentadienyl–Cycloheptatrienyl Titanium Complexes (Troticenophanes)

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Insertion of [Pt(PEt3)2] into a Strained Si−C Bond of Diphenylsila[1]molybdarenophane

Cited by 9 publications

References 32 publications

Reactions of Hydrosilanes with Transition Metal Complexes

Reactions of Hydrosilanes with Transition Metal Complexes

ansa-Zirconocenes with Aluminum or Gallium in Bridging Positions

Synthesis and Reactivity of Boron‐, Silicon‐, and Tin‐Bridged ansa‐Cyclopentadienyl–Cycloheptatrienyl Titanium Complexes (Troticenophanes)

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Insertion of [Pt(PEt₃)₂] into a Strained Si−C Bond of Diphenylsila[1]molybdarenophane