Occurrence of a µ-SiF interaction in bimetallic trifluorosilyl complexes

Braunstein, Pierre; Colomer, Ernesto; Knorr, Michael; Tiripicchio, António; Camellini, Marisa Tiripicchio

doi:10.1039/dt9920000903

Cited by 24 publications

(9 citation statements)

References 29 publications

(4 reference statements)

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“…Structural data reported for silyl−transition-metal complexes prepared from hydrosilanes and that include only those derivatives with “classical” M−Si, M−H, and/or Si−H bonds are summarized in Table . − …”

Section: Solid-state Structuresmentioning

confidence: 99%

“…Si(Fe,Ru,Os) bonds prepared by other methods or preceding 1980 and structurally characterized. SiFe: 2.218(2); 2.222(3); , 2.224(1); 2.2277(14); 2.230(2); 2.2330(14); 2.249(1); , 2.249(3); 2.252(3); 2.258(1); 2.260(6); 2.262(2); , 2.262(1); 2.263(1); 2.263(2), 2.264(2); 2.264(2); 2.265(1); 2.266(3); 2.267(1); 2.268(8); 2.271(4); 2.275(2); 2.278(1); 2.280(3); 2.281(4); 2.285(3); 2.286(5); 2.286(1); 2.287(2); 2.290(3); 2.294(1); 2.296(2); 2.297(3); 2.301(1); 2.303(1); 2.307(1); 2.307(2); 2.310(1); 2.322(1); 2.311(2); 2.311(3); 2.3l3(6); 2.315(2); 2.316(13); 2.322(4); 2.325(3); 2.326(3); 2.327(3); 2.328(1); 2.33(1); 2.330(2); 2.338(4); 2.339(2); 2.339(1); 2.341(2); 2.346; 2.347(1); 2.350(1); 2.354(2); 2.356; 2.356(1); 2.357(3); , 2.364(5); 2.365(2); 2.366(2); 2.366(1); 2.375(2); 2.378(1);…”

Section: Solid-state Structuresunclassified

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Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

1998

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Section: Solid-state Structuresmentioning

confidence: 99%

Section: Solid-state Structuresunclassified

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

1998

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“…This feature has been studied in detail, dation of the liberated PPh 3 , since a singlet at δ ϭ 29.5 due to minor amounts of OϭPPh 3 was also detected in the 31 Pboth in solution and in the solid state. [5,8,9] The σ-alkenyl complex 2a is also formed using the Ph 2 MeP-substituted NMR spectrum.…”

Section: )] 1c As Pre-[(oc) 3 Fe{si(ome) 3 }(µ-Dppa)pt(h)(pph 3 )]mentioning

confidence: 99%

Reactivity of Silyl-Substituted Heterobimetallic Iron–Platinum Hydride Complexes towards Unsaturated Molecules, I Alkyne Insertions into the Platinum-Hydride Bond, Phosphane-Induced σ-Alkenyl–μ-Vinylidene Rearrangements and Formation of μ-Isonitrile Complexes

Knorr

Strohmann

2000

Eur. J. Inorg. Chem.

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The heterobimetallic hydride complexes [(OC)3Fe{Si(OMe)3}(μ‐Ph2PXPPh2)Pt(H)(PR3)] (1a: X = CH2, PR3 = PPh3; 1b: X = NH, PR3 = PPh3; 1c: X = CH2, PR3 = PMePh2) have been prepared by the oxidative addition of [(OC)3Fe(H){Si(OMe)3}(η1‐Ph2PXPPh2)] to [Pt(H2CCH2)(PPh3)2] or by reaction of K[(OC)3Fe{Si(OMe)3}(η1‐dppm)] with trans‐[Pt(Cl)(H)(PPh3)2]. The solid‐state structure of compound 1b has been determined by single‐crystal X‐ray diffraction. 1‐Alkynes such as methylpropiolate or phenylacetylene insert in a regiospecific manner into the Pt–H bond of 1 to yield the σ‐alkenyl complexes [(OC)3Fe{μ‐Si(OMe)2(OMe)}(μ‐Ph2PXPPh2)Pt{C(R)=CH2}] (2a: X = CH2, R = CO2Me; 2b: X = NH, R = CO2Me; 3a: X = CH2, R = Ph). Addition of the Pt–H bond of 3a across the triple bond of [D1]phenylacetylene affords [(OC)3Fe{μ‐Si(OMe)2(OMe)}(μ‐dppm)Pt{C(Ph)=C(D)H}] (3a*) having the deuteron trans to platinum (cis addition). This insertion reaction is accompanied by dissociation of the platinum‐bonded PR3 ligand and saturation of the vacant coordination site by a dative μ‐η2‐Si–O→Pt interaction. When 3 is treated with PR3 again, a subsequent phosphane‐induced rearrangement leading to vinylidene‐bridged complexes [(OC)3Fe{μ‐CC(H)R′}(μ‐Ph2PXPPh2)Pt(PR3)] (4a: X = CH2, R′ = Ph, PR3 = PPh3; 4b: X = NH, R′ = Ph, PR3 = PPh3; 4c: X = CH2, R′ = Ph, PR3 = PMePh2; 4d: X = CH2, R′ = p‐tolyl, PR3 = PPh3) occurs. Upon purging a solution of 3a with carbon monoxide, the labile CO adduct [(OC)3Fe{Si(OMe)3}(μ‐dppm)‐Pt(CO){C(Ph)=CH2}] 5a is formed, addition of 2,6‐xylyl isocyanide to 2a and 3a affords the isonitrile adducts [(OC)3Fe{Si(OMe)3}(μ‐dppm)Pt(CNxylyl){C(R)=CH2}] (5b: R = CO2Me; 5c: R = Ph), respectively. When hydride complex 1a is allowed to react with stoichiometric amounts of aromatic isonitriles, formal elimination of HSi(OMe)3 occurs, yielding the heterodinuclear isonitrile‐bridged complexes [(OC)3Fe(μ‐C=N‐R)(μ‐dppm)Pt(PPh3)] (6a: R = 2,6‐xylyl; 6b: R = o‐anisyl; 6c: R = p‐anisyl; 6d: R = p‐C6H4NH2) and the bis(isonitrile) complexes [(OC)2(RN≡C)Fe(μ‐C=N–R)(μ‐dppm)Pt(PPh3)] (7a: R = 2,6‐xylyl; 7b: R = p‐anisyl). Single‐crystal X‐ray diffraction studies perfomed on 6a and 6b reveal that the molecular structures of these μ‐isonitrile complexes closely resemble the μ‐vinylidene complexes 4. The two metal centers are bridged in a symmetric manner by strongly bent CNR ligands, the aromatic groups R being oriented towards the Fe(CO)3 moiety. Electrophilic addition of HBF4 to the basic nitrogen atom of the μ‐CNR ligand transforms 6 to the cationic μ‐aminocarbyne complexes [(OC)3Fe{μ‐CN(H)R}(μ‐dppm)Pt(PPh3)][BF4] (8a: R = 2,6‐xylyl; 8b: R = p‐anisyl; 8c: R = p‐C6H4NH2).

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“…It is noteworthy that bimetallic catalysts have been applied to various organic reactions in the recent past and often such catalysts offered superior results in terms of efficiency and selectivity relative to the individual ones . Although, there exist some well‐characterized bimetallic Fe–Pd complexes in the literature, such complexes have not been investigated so far as catalysts for the Suzuki–Miyaura reactions. Thus, in order to enlarge this series and to widen the scope of metal‐containing phosphines as ligands, herein we have also explored the catalytic efficiency of the complex 1 /PdCl 2 system for the Suzuki–Miyaura cross‐coupling reactions of aryl halides with arylboronic acids.…”

Section: Introductionmentioning

confidence: 99%

Iron carbonyl complex containing bis[2‐(diphenylphosphino)phenyl]ether enhancing efficiency in the palladium‐catalyzed Suzuki–Miyaura reaction

Borah

Bhattacharyya

Das

2012

Applied Organom Chemis

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The reaction of [Fe3(CO)12] with bis[2‐(diphenylphosphino)phenyl]ether (DPEphos) in refluxing THF afforded a mononuclear complex, [Fe(CO)4(η1‐P‐DPEphos)] (1), as major product and a binuclear complex, [Fe2(CO)6(μ‐CO)(μ‐P,P‐DPEphos)] (2), as minor product respectively. The DPEphos ligand acts as a terminal P‐donor in complex 1 and a bridging P,P‐donor in complex 2. Complexes 1 and 2 were characterized by elemental analysis, fast atom bombardment mass spectrometry, FT‐IR, 1H and 31P{1H} NMR spectroscopy. The structure of complex 1 has been tentatively assigned by density functional theory calculations and its analogy with reported complexes. Combination of complex 1 and PdCl2 furnished an active catalyst for the Suzuki–Miyaura cross‐coupling reactions of various aryl halides with arylboronic acids. Interestingly, under the same experimental condition, complex 1/PdCl2 as catalyst showed superior activity over the DPEphos/PdCl2 system. Copyright © 2012 John Wiley & Sons, Ltd.

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Occurrence of a µ-SiF interaction in bimetallic trifluorosilyl complexes

Cited by 24 publications

References 29 publications

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds

Reactivity of Silyl-Substituted Heterobimetallic Iron–Platinum Hydride Complexes towards Unsaturated Molecules, I Alkyne Insertions into the Platinum-Hydride Bond, Phosphane-Induced σ-Alkenyl–μ-Vinylidene Rearrangements and Formation of μ-Isonitrile Complexes

Iron carbonyl complex containing bis[2‐(diphenylphosphino)phenyl]ether enhancing efficiency in the palladium‐catalyzed Suzuki–Miyaura reaction

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