54775-87-0

Upstream product

• 67969-82-8 tetrafluoroboric acid diethyl ether 
• 32109-09-4 [MoH₄(1,2-bis(diphenylphosphino)ethane)2] 
• 16887-00-6 chloride 
• 7647-01-0 hydrogenchloride 
• 4206-75-1 phenylchlorosilane 
• 75-77-4 chloro-trimethyl-silane 

Downstream Products

• 32109-09-4 [MoH₄(1,2-bis(diphenylphosphino)ethane)2] 

Relevant academic research and scientific papers

Reactions of molybdenum tetrahydrido complex with halohydrosilanes

The thermal reactions of [MoH4(dppe)2](1, dppe = Ph2PCH2CH2PPh2)with RSiH 2Xafford [MoH2X(dppe)-{[Ph2PCH 2CH2P(Ph)C6H4-o]RXSi-P,P,Si}](R = Ph, X = Cl (5a); R = cycfo-C6H11, X = Cl (5b); and R = Ph, X = Br (6)) by activation of the Si-H bond of the silanes and the ortho C-H bond of the phenyl group in the dppe ligand. Reduction of the Si-Cl and Mo-Cl bonds in 5a with LiAlH4 leads to the formation of the original complex 1 as a result of unusual Si-C bond cleavage. Meanwhile, dehalogenative reduction of 5a using zinc metal gives the known compound [MoH 3{[Ph2PCH2CH2P(Ph)C 6H4-o]2(Ph)Si-P,P,P,P,Si}](2). The experimental results reported herein provide certain evidence for the involvement of the silylene species in the unusualformation of the present polydentate phosphinoalkyl-silylligands.

Protonation of Unsaturated Hydrocarbon Ligands: Regioselectivity, Stereoselectivity, and Product Specificity

Understanding the mechanisms of pro-tonation of hydrocarbon ligands is fundamental to a wide range of chemistry including organic synthesis, organo-metallic chemistry, and even bioinor-ganic chemistry. Protonation at carbon or metal sites is often slow, with the result that in species containing both types of sites, initial protonation can be at either the metal or the carbon. This has fundamental consequences on the reactivity of hydrocarbon ligands, which are highlighted in this article. In particular, many reactions are apparently the result of a regioselective protonation on the basis of structural analysis of the isolated products. In fact, these products are often formed by an indirect route involving kinetically controlled protona-tion at the wrong site followed by rearrangement to form the thermodynamically controlled, apparently regioselec-tive, product. Other aspects of the pro-tonation mcchanisms of complexes containing hydrocarbon ligands are discussed, with an emphasis on the manner in which competitive protonation at metal or ligand can be exploited to select which hydrocarbon is produced and to control the stereochemistry of the hydrocarbon.

Preparation and Reactions of 3-C4H7)(Ph2PCH2CH2PPh2-κ2P)(Ph2PCH2CH2PPh2-κP)>: the Intramolecular Interconversion between η3-2-Methylallyl and η4-Trimethylenemethane Ligands

The complex 3-C4H7)(dppe-κ2P)(dppe-κP)> (dppe = Ph2PCH2CH2PPh2) has been prepared.Variable-temperature 1H, 13C and 31P NMR spectroscopy demonstrates that this 16-electron, η3-2-methylallyl species (the dominant form at 25 deg C) rapidly interconverts, intramolecularly, to the 18-electron, η4-trimethylenemethane species, 4-C4H6)(dppe-κ2P)(dppe-κP)> (the dominant form at -80 deg C).Protonation of 3-C4H7)(dppe-κ2P)(dppe-κP)> with HCl at 25 deg C gives stoichiometric yields of 2P)2> and t-BuCH2C(Me)CH2.Stopped-flow spectrophotometric studies of the protonation reaction indicate that the alkene formation involves rapid protonation of the molybdenum to give 3-C4H7)(dppe-κ2P)(dppe-κP)>(+), which undergoes rate-limiting intramolecular hydrogen migration to form 2-Me2C=CH2)(dppe-κ2P)2>(+).Subsequent formation of t-BuCH2C(Me)=CH2 occurs rapidly and is not amenable to kinetic analysis.However, the dimerisation is too fast to be catalysed by the excess of HCl alone, and a mechanism involving formation of t-BuCH2C(Me)=CH2 at the molybdenum centre is proposed.

Selective Formation of Propyne by Protonation of an Allyl Complex

Treatment of 3-C3H5)(Ph2PCH2CH2PPh2)2> with a large excess of anhydrous HCl in tetrahydrofuran rapidly yields and propyne, at low concentrations of acid, propene is formed; the mechanism of these reactions has been established by detailed kinetic studies and product analyses.

The Detection and Reactivity of 2-H2)(Ph2PCH2CH2PPh2)2>2+

The reaction between and HCl in tetrahydrofuran involves the detected, transient intermediate, 2-H2)(Ph2PCH2CH2PPh2)2>2+, a species which must contain at least one co-ordinated dihydrogen molecule if the maximum oxidation state of the molybdenum is not to be exceeded; the reactivity of polyhydridic sites towards protons, particularly with respect to the dinitrogen-binding site in the enzyme nitrogenase, is discussed in the light of this study.

Reactions of molybdenum hydrides with organochlorosilanes: Silicon-silicon bond formation under mild conditions

Reactions of molybdenum hydrides containing polydentate phosphinoalkylsilyl ligands with a number of chlorosilanes have been investigated; this has led to the discovery of a novel type of a dechlorinative Si-Si coupling reaction.

Preparation, structures, and some reactivities of five-coordinate alkyne complexes of mo with tetraphosphine or diphosphine coligand [mo(rc≡cr ){mes0-0-c6h4(pphch2ch2pph 2)2}] and [mo(rc≡cr

The five-coordinate alkyne complexes [MO(η2-RC≡CR )(κ4-P4)] (3; P4 = meso-o-C6H4(PPhCH 2CH2PPh2)2) were synthesized by treatment of the Mo(0) tetraphosphine complex [M

Metal hydrides as intermediates in the reactions of coordinated unsaturated hydrocarbons: Formation of propyne by protonation of trans-[WH(η3-C3H5)(Ph2PCH 2CH2PPh2)2]

The reaction of anhydrous HCl with trans-[WH(η3-C3H5)(dppe)2] (dppe = Ph2PCH2CH2PPh2) in tetrahydrofuran gives [WH2Cl2-(dppe)2] togeth

Protonation of an internal alkyne produces a terminal alkene: Reactivity of [Mo(η2-MeCCMe)(Ph2PCH2CH 2PPh2)2]

Structurally defined [Mo(η2-MeCCMe)-(Ph2PCH2CH 2PPh2)2] reacts with anhydrous HCl in thf to give predominantly trans-[MoCl2(Ph2PCH2CH2PPh 2)2] with but-1-ene (69 ± 6%) and cis-but-2-ene (10 ± 2%); in addition, some [MoH2Cl2(Ph2PCH2CH 2PPh2)2] and but-2-yne (21 ± 5%) are produced; the mechanistic features by which protonation of an internal alkyne yields a terminal alkene are enumerated.

Rapid binding and activation of small molecules by in the presence of HBF4*OEt2. Crystal structure of the product obtained with phenylacetylene trans-2-PhCCH)(Ph2PCH2CH2PPh2)2>BF4

In the presence of HBF4*OEt2, exhibits a remarkably rapid and diverse range of reactions with a variety of small molecules.The crystal structure of the product obtained in the presence of phenylacetylene, trans-2-PhCCH)(Ph2PCH2CH2PPh2)2>BF4 is reported.