Ruthenium-Mediated Insertion of an Unsaturated C4 Unit into the P−N Bond of an Aminophosphine Ligand

Abstract

The reactions of 1,6-heptadiyne and 1,7-octadiyne with [RuCp(PPh2NEt2)(CH3CN)2]+ afford the η3-phosphaallyl−η2-vinylamine complexes [RuCp(η3(P,C,C)-PPh2CHC(CH2) n -η2(C,C)-CCHNEt2)]+ (n = 3, 4), which cleanly rearrange to give the η1-phosphaallyl−η3-azaallyl complexes [RuCp(η1(P)-PPh2CHC(CH2) n -η3(C,C,N)-CCHNEt2)]+ (n = 3, 4).

Noble metals

“…59 The coordinatively unsaturated 16 electron cationic [Cp*Ru(k 2 -P,N-HL)] and zwitterionic [Cp*Ru(k 2 -P,N-L)] [HL = 1-P i Pr 2 -2-NMe 2 -indene and 2-NMe 2 -3-P i Pr 2 -indene] complexes have been isolated and show ligand-assisted double-geminal C-H bond activation and reversible a-H elimination. 60 Similarly, rutheniummediated insertion of an unsaturated C4 unit into the P-N bond of an aminophosphane ligand has been observed with 6-heptadiyne and 1,7-octadiyne and 61 Reaction between [7-( t BuNH)-7,8,9-C 3 B 8 H 10 ] À and [Cp*RuCl] 4 leads to the ruthenatricarbollide [1-Cp*-12-( t BuNH)-1,2,4,12-RuC 3 B 8 H 10 ] and causes extensive polyhedral rearrangement, which occurs under very mild conditions and brings the carbon atoms to positions of maximum separation within the framework; further rearrangement occurs under reflux in xylene. 62 Acetonitrile induces a clean isomerization of the amido-bridged complex [(Cp*Ru) 2 {m 2 -k 2 :Z 4 -2,3-naphthalenediamido}] into the k 2 :Z 6 -bonded dinuclear complex [Cp*Ru{m 2 -k 2 :Z 6 -2,3-naphthalenediamido}RuCp*] featuring a coordinatively unsaturated {Cp*Ru} terminal diamide fragment.…”

Reactions of Ruthenium–Aminophosphane Complexes with Diynes: P–N Bond Activation and Formation of Novel Phosphaallyl, Azaallyl, and Aminocarbene Complexes

“…In contrast to 1a-c, the reaction of 2a both with 1,6-heptadiyne and 1, 7- + (R = Ph, iPr, RЈ = Ph, C 6 F 5 ). [10,11] Compounds 6a and 6b are air-stable both in solution and in the solid state and were characterized by 1 H, 13 C{ 1 H}, and 31 P{ 1 H} NMR spectroscopy as well as elemental analysis. As these compounds exhibit similar spectroscopic features to the RuCp η 4 -butadiene amido complexes already described recently, [10,11] they are not discussed here.…”

“…[RuCp-(PPh 2 NEt 2 )(CH 3 CN) 2 ] + , we discovered that it reacts with diynes to afford unusual and unprecedented phosphaallyl complexes which readily rearrange to give azaallyl complexes. [11] This process formally constitutes an insertion of an unsaturated carbon C4 chain into the P-N bond, that is, in the course of this reaction the P-N bond is cleaved. …”

(η3-Allyl)bromo(η5-cyclopentadienyl)(phenylaminodiphenylphosphine-κP)ruthenium(IV) hexafluorophosphate

“…Ruthenium complexes with cyclopentadienyl (Cp), pentamethylcylopentadienyl (Cp*) or hydridotrispyrazolylborate (Tp) as ancillary ligand and phenylaminodiphenylphosphine (Ph 2 PNHPh) as coligand have recently attracted attention because of a rich chemistry in stoichiometric or catalytic transformations of alkenes and alkynes (Pavlik et al, 2003(Pavlik et al, , 2006Pavlik, Jantscher et al, 2005;Priya et al, 2003;Jimenez-Tenorio et al, 2005). For Cp, such compounds are accessible from the cationic complex [RuCp(Ph 2 PNHPh)(CH 3 CN) 2 ] + (Pavlik et al, 2003), which behaves as a masked electron-deficient entity and reacts under mild conditions with unsaturated hydrocarbons.…”