The UV‐Light Initiated Reaction of Organosilanes with Tungsten Hexacarbonyl: Formation of an Organosilylene Complex and Organosilylium Salts

Dannappel, Kai; Nienhaus, Roland; Schürmann, Markus; Costisella, B.; Jurkschat, Klaus

doi:10.1002/zaac.200900204

Cited by 21 publications

(11 citation statements)

References 84 publications

(43 reference statements)

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“…The products that have been obtained from the reactions of hydrosilanes with transition metal complexes are summarized in Tables (primary silanes), − (secondary silanes), ,− ,, and (tertiary silanes)primarily for products that contain a Si–TM bond. Some researchers study reactions of primary and/or secondary and/or tertiary silanes.…”

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

“…Additional derivatives formed at 110 °C: R = c -C 6 H 11 , X = Cl (74%), R = Ph, X = Br (80%) 10 R = t Bu-2,6-[P(O)(O i Pr) 2 ] 2 C 6 H 2 - 11 Other secondary silanes, Ph 2 SiH 2 , Et 2 SiH 2 , and MesClSiH 2 did not react.…”

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

“… 21 The sign on the J SiH was determined and is negative and thus indicates direct Si−H bonding 22 R = t Bu-2,6-[P(O)(O i Pr) 2 ] 2 C 6 H 2 - 23 Additional derivative, R = Me …”

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

“… 7 Formed from reaction of H 3 SiPh 8 Hydrogen atoms were placed in calculated positions. ,, 9 Hydrogen atoms were placed in geometrically calculated positions using a riding model with constrained isotropic temperature factors 10 Hydride was located from Fourier difference synthesis and positionally refined isotropically …”

Section: Solid State Structuresmentioning

confidence: 99%

“… 9 Hydrogen atoms were placed in geometrically calculated positions using a riding model with constrained isotropic temperature factors …”

Section: Solid State Structuresmentioning

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: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

“… 21 The sign on the J SiH was determined and is negative and thus indicates direct Si−H bonding 22 R = t Bu-2,6-[P(O)(O i Pr) 2 ] 2 C 6 H 2 - 23 Additional derivative, R = Me …”

Section: Reactions Of Hydrosilanes With Transition Metal Complexesmentioning

confidence: 99%

Section: Solid State Structuresmentioning

confidence: 99%

“… 9 Hydrogen atoms were placed in geometrically calculated positions using a riding model with constrained isotropic temperature factors …”

Section: Solid State Structuresmentioning

confidence: 99%

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Reactions of Hydrosilanes with Transition Metal Complexes

2016

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Hydrosilylation Induced by N→Si Intramolecular Coordination: Spontaneous Transformation of Organosilanes into 1‐Aza‐Silole‐Type Molecules in the Absence of a Catalyst

Novák

Dostál

Alonso

et al. 2014

Chemistry A European J

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Our attempts to synthesize the N→Si intramolecularly coordinated organosilanes Ph2 L(1) SiH (1 a), PhL(1) SiH2 (2 a), Ph2 L(2) SiH (3 a), and PhL(2) SiH2 (4 a) containing a CH=N imine group (in which L(1) is the C,N-chelating ligand {2-[CH=N(C6 H3 -2,6-iPr2)]C6 H4}(-) and L(2) is {2-[CH=N(tBu)]C6 H4}(-)) yielded 1-[2,6-bis(diisopropyl)phenyl]-2,2-diphenyl-1-aza-silole (1), 1-[2,6-bis(diisopropyl)phenyl]-2-phenyl-2-hydrido-1-aza-silole (2), 1-tert-butyl-2,2-diphenyl-1-aza-silole (3), and 1-tert-butyl-2-phenyl-2-hydrido-1-aza-silole (4), respectively. Isolated organosilicon amides 1-4 are an outcome of the spontaneous hydrosilylation of the CH=N imine moiety induced by N→Si intramolecular coordination. Compounds 1-4 were characterized by NMR spectroscopy and X-ray diffraction analysis. The geometries of organosilanes 1 a-4 a and their corresponding hydrosilylated products 1-4 were optimized and fully characterized at the B3LYP/6-31++G(d,p) level of theory. The molecular structure determination of 1-3 suggested the presence of a Si-N double bond. Natural bond orbital (NBO) analysis, however, shows a very strong donor-acceptor interaction between the lone pair of the nitrogen atom and the formal empty p orbital on the silicon and therefore, the calculations show that the Si-N bond is highly polarized pointing to a predominantly zwitterionic Si(+) N(-) bond in 1-4. Since compounds 1-4 are hydrosilylated products of 1 a-4 a, the free energies (ΔG298), enthalpies (ΔH298), and entropies (ΔH298) were computed for the hydrosilylation reaction of 1 a-4 a with both B3LYP and B3LYP-D methods. On the basis of the very negative ΔG298 values, the hydrosilylation reaction is highly exergonic and compounds 1 a-4 a are spontaneously transformed into 1-4 in the absence of a catalyst.

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Novel Transition‐Metal (M=Cr, Mo, W, Fe) Carbonyl Complexes with Bis(guanidinato)silicon(II) Ligands

Mück

Kloß

Baus

et al. 2014

Chemistry A European J

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The donor-stabilized silylene 2 (the first bis(guanidinato)silicon(II) complex) reacts with the transition-metal carbonyl complexes [M(CO)6 ] (M=Cr, Mo, W) to form the respective silylene complexes 7-10. In the reactions with [M(CO)6 ] (M=Cr, Mo, W), the bis(guanidinato)silicon(II) complex 2 behaves totally different compared with the analogous bis(amidinato)silicon(II) complex 1, which reacts with [M(CO)6 ] as a nucleophile to replace only one of the six carbonyl groups. In contrast, the reaction of 2 leads to the novel spirocyclic compounds 7-9 that contain a four-membered SiN2 C ring and a five-membered MSiN2 C ring with a MSi and MN bond (nucleophilic substitution of two carbonyl groups). Compounds 7-10 were characterized by elemental analyses (C, H, N), crystal structure analyses, and NMR spectroscopic studies in the solid state and in solution.

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The UV‐Light Initiated Reaction of Organosilanes with Tungsten Hexacarbonyl: Formation of an Organosilylene Complex and Organosilylium Salts

Abstract: Dedicated to Professor Michael Veith on the occasion of his 65th birthday.

Cited by 21 publications

References 84 publications

Reactions of Hydrosilanes with Transition Metal Complexes

Reactions of Hydrosilanes with Transition Metal Complexes

Hydrosilylation Induced by N→Si Intramolecular Coordination: Spontaneous Transformation of Organosilanes into 1‐Aza‐Silole‐Type Molecules in the Absence of a Catalyst

Novel Transition‐Metal (M=Cr, Mo, W, Fe) Carbonyl Complexes with Bis(guanidinato)silicon(II) Ligands

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