14630-40-1Relevant articles and documents
Mechanism-based design of labile precursors for chromium(i) chemistry
Akturk, Eser S.,Yap, Glenn P. A.,Theopold, Klaus H.
, p. 15402 - 15405 (2015)
Dinitrogen complexes of the type TpR,RCr-N2-CrTpR,R are not the most labile precursors for Cr(i) chemistry, as they are sterically protected from obligatory associative ligand substitution. A mononuclear alkyne complex-TptBu,MeCr(η2-C2(SiMe3)2)-proved to be much more reactive.
REACTION OF GERMYLENE WITH THIOKETENES: SYNTHESIS OF ALKYLIDENEDIGERMATHIETANES
Ando, Wataru,Tsumuraya, Takeshi,Goto, Midori
, p. 5105 - 5108 (1986)
In the reaction of dimethyl- or diphenylgermylene with di-tert-butyl-thioketene alkylidenedigermathietanes were obtained, probably via alkylidenegermathiiranes.The exact structure of alkylidenedigermathietane 2b was confirmed by X-ray crystal analysis.
THE STEREOCHEMISTRY OF ORGANOMETALLIC COMPOUNDS. XXXVI. REGIO- AND STEREO-CHEMICAL CONTROL IN THE NICKEL-CATALYSED HYDROCYANATION OF SILYLALKYNES
Fitzmaurice, Neil J.,Jackson, W. Roy,Perlmutter, Patrick
, p. 375 - 382 (1985)
The regioselectivity of hydrocyanation of silylalkynes can be controlled by varying the size of the groups attached to silicon leading, for example, to efficient preparations of E-3-trialkylsilyl-2-alkyl-2-alkenenitriles.High yields of the silylalkene nitriles can be obtained by using either acetone cyanohydrin or hydrogen cyanide as reagents.
Phosphinidene Reactivity of a Transient Vanadium P≡N Complex
Courtemanche, Marc-André,Transue, Wesley J.,Cummins, Christopher C.
, p. 16220 - 16223 (2016)
Toward the preparation of a coordination complex of the heterodiatomic molecule PN, P≡N-V(N[tBu]Ar)3 (1, Ar = 3,5-Me2C6H3), we report the use of ClPA (A = C14H10, anthracene) as a formal source of phosphorus(I) in its reaction with Na[NV(N[tBu]Ar)3] (Na[4]) to yield trimeric cyclo-triphosphane [PNV(N[tBu]Ar)3]3 (3) with a core composed exclusively of phosphorus and nitrogen. In the presence of NapS2 (peri-1,8-naphthalene disulfide), NapS2P-NV(N[tBu]Ar)3 (6) is instead generated in 80% yield, suggesting trapping of transient 1. Upon mild heating, 3 readily fragments into dimeric [PNV(N[tBu]Ar)3]2 (2), while in the presence of bis(trimethylsilyl)acetylene or cis-4-octene, the respective phosphirene (Ar[tBu]N)3VN-PC2(SiMe3)2 (7) or phosphirane (Ar[tBu]N)3VN-P(C8H16) (8) compounds are generated. Kinetic data were found to be consistent with unimolecular decay of 3, and [2+1]-cycloaddition with radical clocks ruled out a triplet intermediate, consistent with intermediate 1 reacting as a singlet phosphinidene. In addition, both 7 and 8 were shown to reversibly exchange cis-4-octene and bis(trimethylsilyl)acetylene, serving as formal sources of 1, a reactivity manifold traditionally reserved for transition metals.
Tetrasilyl-substituted cyclobutadiene dianion dilithium salt: Synthesis and structure
Sekiguchi,Matsuo,Tanaka,Watanabe,Nakamoto
, p. 1109 - 1115 (2004)
The reaction of tetrakis(trimethylsilyl)cyclobutadienylcyclopentadienyl cobalt complex (Me3Si)4C4CoCp with lithium metal in THF yielded the dilithium salt of cyclobutadiene dianion CBD 2- stabilized by four trimethylsilyl groups, Li+ 2[(Me3Si)4C4]2-. The bridged CBD2- dianion was also synthesized by a similar procedure starting from the bridged cobalt complex, which was prepared from the reaction of 2,2,5,5,8,8,11,11-octamethyl-2,5,8,11-tetrasilacyclododeca-1,6-diyne with CpCo(CO)2 in refluxing octane. The aromaticity of the CBD 2- is discussed on the basis of the structural characteristics and magnetic properties.
Et2Zn-mediated stoichiometric C(sp)-H silylation of 1-alkynes and chlorosilanes
Huang, Pan,Xu, Dawen,Reich, Robert M.,Kaiser, Felix,Liu, Boping,Kühn, Fritz E.
supporting information, p. 1574 - 1577 (2019/05/17)
A first example of an Et2Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis.
Synthesis, Characterization, and Reactivity of an Ethynyl Benziodoxolone (EBX)-Acetonitrile Complex
Yudasaka, Masaharu,Shimbo, Daisuke,Maruyama, Toshifumi,Tada, Norihiro,Itoh, Akichika
supporting information, p. 1098 - 1102 (2019/05/16)
The synthesis of a crystalline ethynyl-1,2-benziodoxol-3(1H)-one (EBX)-acetonitrile complex is described. EBX has been widely used as an active species for a variety of reactions; however, its high instability has so far prevented its isolation. The EBX-acetonitrile is self-assembled into a double-layered honeycomb structure through weak hypervalent iodine secondary interactions and hydrogen bonding. The N-ethynylation of a variety of sulfonamides using the EBX-acetonitrile complex as a substrate under mild conditions is also described.
Catalytic Selective Metal-Free Cross-Coupling of Heteroaromatic N-Oxides with Organosilanes
Puthanveedu, Mahesh,Polychronidou, Vasiliki,Antonchick, Andrey P.
, p. 3407 - 3411 (2019/05/10)
A metal-free, regioselective C-H functionalization of heteroaromatic N-oxides has been developed. The method enables the synthesis of various benzylated and alkynylated N-heterocycles in a transition-metal-free manner employing organosilanes as coupling partners. The unanticipated reactivity has been exploited for the synthesis of a number of symmetrical disubstituted acetylenes from ethynyltrimethylsilane via carbon-silicon bond metathesis.
Metal Acetylide Elimination: The Key Step in the Cascade Decomposition and Transformation of Metalated Propargylamines
Flynn, Matthew T.,Blair, Victoria L.,Andrews, Philip C.
supporting information, p. 1225 - 1228 (2018/04/30)
Metal acetylide elimination facilitates a novel one-pot cascade metalation and elimination/addition route to a series of unsymmetrical secondary amines from the reaction of secondary propargylamines with organometallic reagents. Spectroscopic evidence suggests a dimetalated amido intermediate rather than an allene.
Facile access to tuneable Schwartz's reagents: Oxidative addition products from the reaction of amide N-H bonds with reduced zirconocene complexes
Haehnel, Martin,Yim, Jacky C.-H.,Schafer, Laurel L.,Rosenthal, Uwe
supporting information, p. 11415 - 11419 (2013/11/06)
On the tracks of Schwartz's reagent: Two zirconocene hydrido amidate complexes are synthesized by formal oxidative addition of amide N-H bonds to reduced zirconocene fragments. Insertion reactions with alkenes show a different behavior than Schwartz's reagent by forming branched insertion products. The insertion product and the hydrido complex are characterized by X-ray analysis. Copyright
