A silicon–carbonyl complex stable at room temperature

Ganesamoorthy, Chelladurai; Schoening, Juliane; Wölper, Christoph; Song, Lijuan; Schreiner, Peter R.; Schulz, Stephan

doi:10.1038/s41557-020-0456-x

Cited by 88 publications

(84 citation statements)

References 52 publications

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“…[19][20][21] The CO adduct of a gallium-substituted silylene has been isolated. 22 No coupling products were observed. Only through the inclusion of cooperative strategies has CO coupling been observed with these reagents.…”

Section: Dalton Transactionsmentioning

confidence: 95%

Cooperative strategies for CO homologation

Kong

Crimmin

2020

Dalton Trans.

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Section: Dalton Transactionsmentioning

confidence: 95%

Cooperative strategies for CO homologation

Kong

Crimmin

2020

Dalton Trans.

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“…The singlet–triplet energy gap (10.5 kJ/mol) for bis(silyl)silylene 40 is small due to the effect of the electropositive bulky silyl substituents. Very recently, the groups of Schulz and Schreiner reported H 2 splitting by a silylene intermediate :Si[Ga(Br)L] 2 (L = HC[C(Me)N(2,6‐ i Pr 2 C 6 H 3 )] 2 ) ( 46 ) . The treatment of [L(Br)Ga] 2 SiBr 2 with an equimolar amount of LGa at 60 °C under H 2 resulted in the formation of the dihydrosilane H 2 Si[Ga(Br)L] 2 ( 47 ).…”

Section: Small Molecule Activation With Acyclic Silylenesmentioning

confidence: 99%

“…Recently, the groups of Schulz and Schreiner reported the isolation of the silylene carbonyl complex [L(Br)Ga] 2 Si:–CO ( 55 ) (L = HC[C(Me)N(2,6‐ i Pr 2 C 6 H 3 )] 2 ). The reaction of GaL with SiBr 4 under a CO atmosphere, generates the silylene [L(Br)Ga] 2 Si: ( 46 ) in situ, subsequently affording the silylene carbonyl complex 55 . Compound 55 is remarkably stable both in the solid state ( T d = 176–177 °C) and in solution, no decomposition was observed in toluene solution up to 80 °C.…”

Section: Small Molecule Activation With Acyclic Silylenesmentioning

confidence: 99%

Small Molecule Activation by Two‐Coordinate Acyclic Silylenes

Fujimori

Inoue

2020

Eur J Inorg Chem

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In recent decades, the chemistry of stable silylenes (R2Si:) has evolved significantly. The first major development in this chemistry was the isolation of a silicocene which is stabilized by the Cp* (Cp* = η5‐C5Me5) ligand in 1986 and subsequently the isolation of a first N‐heterocyclic silylene (NHSi:) in 1994. Since the groundbreaking discoveries, a large number of isolable cyclic silylenes and higher coordinated silylenes, i.e. Si(II) compounds with coordination number greater than two, have been prepared and the properties investigated. However, the first isolable two‐coordinate acyclic silylene was finally reported in 2012. The achievements in the synthesis of acyclic silylenes have allowed for the utilization of silylenes in small molecule activation including inert H2 activation, a process previously exclusive to transition metals. This minireview highlights the developments in silylene chemistry, specifically two‐coordinate acyclic silylenes, including experimental and computational studies which investigate the extremely high reactivity of the acyclic silylenes.

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“…Very recently, the first synthesis and isolation of a roomtemperature stable carbonyl complex of heavier Group 14 element has been achieved by tuning the substituents on the central element. The groups of Schreiner, Schulz and colleagues 14…”

mentioning

confidence: 99%

“…In addition, complex 10 shows a functionalization reaction of the CO moiety, which is also a prototypical reaction for TM carbonyl complexes. The reaction of 10 with trimethylsilyl azide (Me 3 SiN 3 ) afforded the silyl cyanide [(Me 3 Si) 3 Si]( t Bu 3 Si) Si(OSiMe 3 )(CN) (14). Thus, complexes 7 and 10 show reactivity as TM mimics.…”

mentioning

confidence: 99%

Main group carbonyl complexes

Fujimori

Inoue

2020

Commun Chem

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The chemistry of carbon monoxide (CO) as a ligand has evolved significantly and transition-metal carbonyl complexes have been widely used as catalysts in many important catalytic processes. Here the authors comment on the recent progress of main-group element carbonyl complexes along with their future prospects. Main-group elements belonging to the sand p-blocks of the periodic table contain some of the most abundant elements in the Earth's crust (e.g., silicon and aluminium) and their compounds are manufactured as commercially valuable chemicals. Main-group chemistry has been studied significantly and various main-group compounds in low-valent oxidation states bearing a highenergy highest occupied molecular orbital and an energetically accessible lowest unoccupied molecular orbital are known to mimic the reactivity of transition-metal (TM) complexes such as the activation of small molecules and catalytic reactions. Recently, the chemistry of main-group carbonyl complexes has garnered increased attention. Carbon monoxide (CO), a ubiquitous atmospheric trace gas produced by natural and anthropogenic sources, is a versatile feedstock for chemical or material production and is widely utilized in both academia and industry. In organometallic chemistry, CO is an important ligand (carbonyl) and plays a key role in various catalytic processes. TMs are known to react with CO to form TM carbonyl complexes with various types of TM-CO bonding motifs, e.g., terminal, bridging, and isocarbonyl. The most common TM carbonyl complexes contain terminal CO bonds, which consists of σ-donation from CO lone pair to an empty orbital on the TM and πbackdonation from a filled d orbital of the TM to an empty π*-orbital on CO. These complexes are used as important reagents in various industrial applications such as hydroformylation, the Cativa process, the Fischer-Tropsch process, and the Pauson-Khand reaction 1. Main-group carbonyl complexes Although the formation of carbonyl complexes by the simple reaction with CO is very rare for main-group elements, due to the lack of suitable π-back-bonding orbitals, some milestone advances in main-group carbonyl chemistry have been recently reported. For the s-block elements, only alkaline Earth metal complexes M(CO) 8 (M = Ca, Sr, or Ba), which are isolated in a low-temperature neon matrix, have been reported by the groups of Zhou, Frenking and colleagues 2,3. On the other hand, several examples of isolable p-block carbonyl complexes at ambient temperature have been reported. It is known that Lewis acidic boranes such as BH 3 , HB (C 6 F 5) 2 , and perfluoroalkylboranes react with CO to form the corresponding boron mono

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A silicon–carbonyl complex stable at room temperature

Cited by 88 publications

References 52 publications

Cooperative strategies for CO homologation

Cooperative strategies for CO homologation

Small Molecule Activation by Two‐Coordinate Acyclic Silylenes

Main group carbonyl complexes

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