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C–H vs. N–H Bond Activation in Aminophosphane Ligands: Reaction of [Cp*Ru(MeCN) 2 (PR 1 2 NHR 2 )] + (R 1 = Ph, i Pr; R 2 = Ph, C 6 F 5 ) with Alkynes
Author(s) -
JiménezTenorio Manuel,
Puerta M. Carmen,
Valerga Pedro
Publication year - 2005
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200500034
Subject(s) - chemistry , alkyne , stereochemistry , ligand (biochemistry) , medicinal chemistry , ruthenium , moiety , crystallography , catalysis , receptor , biochemistry
The reaction of the complexes [Cp*Ru(MeCN) 2 (PR 1 2 NHR 2 )] + (R 1 = R 2 = Ph 1 ; R 1 = i Pr, R 2 = C 6 F 5 2 ; R 1 = i Pr, R 2 = Ph 3 ) with 1‐alkynes HC≡CR (R = H, n Bu, SiMe 3 ) or diynes HC≡CCH 2 XCH 2 C≡CH (X = O, CH 2 , CH 2 CH 2 ) yields different products depending on the nature of the aminophosphane ligand. In some cases, alkyne coupling involving migration of the phosphane and N–H activation occurs, yielding amidobutadiene complexes of the type [Cp*Ru{η 4 ‐C 4 H 3 (R) 2 PR 1 2 NR 2 ‐κ 1 N }] + or [Cp*Ru{η 4 ‐C 4 H 3 (CH 2 XCH 2 )PR 1 2 NR 2 ‐κ 1 N }] + . The complexes [Cp*Ru{η 4 ‐C 4 H 3 (CH 2 OCH 2 )PPh 2 NPh‐κ 1 N }][PF 6 ] ( 1a ) and [Cp*Ru{η 4 ‐C 4 H 3 (CH 2 OCH 2 )P i Pr 2 NC 6 F 5 ‐κ 1 N }][PF 6 ] ( 2a ) have been structurally characterized by X‐ray crystallography. In other cases, for example the reaction of 3 with HC≡CR (R = n Bu, SiMe 3 ), C–H bond activation at the ortho‐ position of the phenyl ring of the phenylamino moiety and coupling to the alkyne fragment takes place. This results in the formation of the novel π‐alkene complexes [Cp*Ru(MeCN){η 2 ‐RCH=CH(C 6 H 4 )NHP i Pr 2 ‐κ 1 P }] + (R = n Bu 4 , SiMe 3 5 ), formally derived from the insertion of the alkyne into the ortho ‐C–H bond of the phenyl ring. The derivative [Cp*Ru(MeCN){η 2 ‐ n BuCH=CH(C 6 H 4 )NHP i Pr 2 ‐κ 1 P }][BPh 4 ] has been structurally characterized by X‐ray crystallography. These compounds are related to the also structurally characterized olefin complex [Cp*Ru(MeCN)(η 2 ‐MeOOCCH=CH 2 )(PPh 2 NHPh)][PF 6 ] ( 6 ), generated by reaction of 1 with methyl acrylate. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)