Insertion of Internal Acetylenes into Orthopalladated a- Methyl benzylami ne. Crystal Structure of [ Pd{C( Ph)=C( Ph)C( Ph)=C( Ph)C,H,CH( Me)NH,}Br]

Vicente, J.; Saura-Llamas, Isabel; Ramírez de Arellano, M. C.

Publication:
Insertion of Internal Acetylenes into Orthopalladated a- Methyl benzylami ne. Crystal Structure of [ Pd{C( Ph)=C( Ph)C( Ph)=C( Ph)C,H,CH( Me)NH,}Br]

dc.contributor.author	Vicente, J.
dc.contributor.author	Saura-Llamas, Isabel
dc.contributor.author	Ramírez de Arellano, M. C.
dc.contributor.department	Química Inorgánica
dc.date.accessioned	2019-11-26T09:14:14Z
dc.date.available	2019-11-26T09:14:14Z
dc.date.created	1995
dc.date.issued	2019-11-26
dc.description.abstract	The complex [Pd{C,H,CH (Me)NH,}( Me,CO),]CIO, reacted with diphenylacetylene to give [ Pd2(q5- C,Ph,),(p-q2-PhC=CPh)]. A pathway for this reaction is suggested. Species related with the postulated intermediates can be isolated starting from [{Pd[C,H,CH( Me) NH,] (p-Br)},] which reacts with disubstituted alkynes (RCECR, R = C0,Me or Ph) to afford [Pd{C(R)=C(R)C(R)=C(R)C,H,CH- (Me)NH,}Br) (R = C0,Me l a or Ph 1 b) through a double insertion of the alkyne into the Pd-C bond. Complex la reacted with 1 equivalent of MeO,CC=CCO,Me to give the tri-insertion reaction product 2. These are the first products of alkyne insertion into a cyclopalladated primary amine. Neutral ligands, such as pyridine (py) or CO, can break the Pd-n-olefinic bond in la to give the corresponding adducts [Pd{C(R)=C(R)C(R)=C(R)C,H,CH(Me)NH,}Br(L)] (R = C0,Me; L = py 3 or CO 4). Complexes l a and 1 b reacted with AgCIO, (1 : 1) in acetone to afford AgBr and [Pd{C(R)=C(R)C(R)=C(R)C,H,CH(Me)NH2}(solv)]CI0, (R = CO,Me, solv = H,O 5a; R = Ph, solv = Me,CO 5b). The reaction of complex la with AgCIO, (1 :1) and excess of pyridine gave the cationic complex [Pd{C(R)=C(R)C(R)=C(R)C,H,CH(Me)NH,}(py),]CIO, 6 (R = C0,Me). The crystal structure of complex l b has been determined by X-ray diffraction. The palladium atom is bonded to Br, N, C(l) and to the midpoint of the C(3)-C(4) double bond in a distorted square-planar geometry.	es
dc.format	application/pdf	es
dc.format.extent	5	es
dc.identifier.uri	http://hdl.handle.net/10201/76962
dc.language	eng	es
dc.rights	info:eu-repo/semantics/openAccess	es
dc.rights	Attribution-NonCommercial-NoDerivatives 4.0 International	*
dc.rights.uri	http://creativecommons.org/licenses/by-nc-nd/4.0/	*
dc.subject	aryl Pd(2) ortometalation amine primary organometallete cyclometallated RX insertion acetyl cyclopentadienyl solvento acetone aquo carbonyl ortometallated
dc.subject.other	CDU::5 - Ciencias puras y naturales::54 - Química::546 - Química inorgánica
dc.title	Insertion of Internal Acetylenes into Orthopalladated a- Methyl benzylami ne. Crystal Structure of [ Pd{C( Ph)=C( Ph)C( Ph)=C( Ph)C,H,CH( Me)NH,}Br]	es
dc.type	info:eu-repo/semantics/article	es
dspace.entity.type	Publication	es