Organoruthenium Complexes Containing New Phosphorus–Carbon and Phosphorus–Carbon–Sulfur Ligands Generated in the Coordination Sphere by Nucleophilic Addition Reactions

Abstract

The reaction of the dimeric complex [RuCl(μ-Cl)(η6-C10H14)]2 (C10H14 = p-cymene) with an excess of allyldiisopropylphosphane (ADIP) leads to the complex [RuCl(η6-C10H14){κ2(P,C)-iPr2PCH2CH(iPr2PCH2CHCH2)CH2}] + (1 + ), which presents a new bidentate κ2(P,C) ligand. The same cationic complex can be prepared by nuclephilic attack of 1 equiv of the free ADIP at the coordinated κ3(P,C,C)-iPr2PCH2CHCH2 ligand in [RuCl(η6-C10H14){κ3(P,C,C)-iPr2PCH2CHCH2}] + (3 + ). Addition of different phosphane ligands to complex 3 + allows to the synthesis of ruthenium complexes with new bidentate ligands κ2(P,C). The unusual complexes [Ru{κ3(P,C,S)-iPr2PCH2CH(SR)CH2}(η6-C10H14)] + (11a–c + ) containing new κ3(P,C,S) ligands can be obtained by the reaction of 3 + with anionic nucleophiles RS–. For comparative purposes, the indenyl complex [Ru(η5-C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}(PPh3)] + (8 + ) has been also prepared and differences in the reactivities of cationic complexes 3 + and 8 + toward nucleophiles are pointed out.

Isomerization Processes on Organoruthenium Complexes Bearing κ2(P,C)‐Bidentate Ligands Generated Through Nucleophilic Addition to Coordinated Alkenyl Phosphanes

“…[7d], As stated before, the 31 P{ 1 H} NMR spectrum of complex 2 in CD 2 Cl 2 shows one signal ( δ = –63.4 ppm) and remains unchanged within a wide range of temperature (–60 to +25 °C). These NMR spectroscopic data agree with a highly diastereoselective generation of the chelate ring [Ru{κ 3 ( P , C , C )‐Ph 2 PCH 2 CH=CH 2 }] as reported by us for the complexes [RuCl(η 6 ‐C 10 H 14 ){κ 3 ( P , C , C )‐ i Pr 2 PCH 2 CH=CH 2 }][BPh 4 ], [Ru(η 5 ‐C 9 H 7 ){κ 3 ( P,C,C )‐Ph 2 PCH 2 CH=CH 2 }(PPh 3 )][PF 6 ],[7f] and [Ru(η 5 ‐C 5 H 5 ){κ 3 ( P,C,C )‐Ph 2 PCH 2 CH=CH 2 }(PPh 3 )][PF 6 ]. [8d]…”

“…The Ru(1)–C(13) bond length [2.146(3) Å] agree with a ruthenium–carbon single bond and with those found for complex [RuCl(η 6 ‐C 10 H 14 ){ĸ 2 ( P , C )‐ i Pr 2 PCH 2 CH( i Pr 2 PCH 2 CH=CH 2 )CH 2 }][BPh 4 ] of 2.142(2) Å …”

“…Thus, the synthesis of complex 2 requires 12 h of reaction, while the ADIP analogue is completed after 2.5 h. In the same way, complex 3 can be dried at high vacuum, while the ADIP analogue removes the MeCN molecule to coordinate the olefin again. Moreover, opening the chelate with pyridine requires higher temperature for the ADIP than for the ADPP ligand …”

“…Complex 6c can be also obtained as the chloride salt through the reaction of the dimeric complex [RuCl(µ‐Cl)(η 6 ‐C 10 H 14 )] 2 with an excess of allyldiphenylphosphane (ADPP) in methanol for two hours at room temperature (Scheme ). The first step for this process must be the formation of the cation of complex 2 in solution and nucleophilic attack of the free ADPP, in the same fashion as it occurs with the analogous product with ADIP ligand …”

“…We have previously reported the synthesis of new half‐sandwich ruthenium(II) complexes bearing the hemilabile allyldiisopropylphosphane (ADIP) and explored their behavior in nucleophilic addition reactions which occur in all cases in a diastereoselective way . In particular, thiolates as anionic S‐donor nucleophiles perform two nucleophilic attacks, both to the olefin and the metal center, giving rise to novel and unprecedented ligands coordinated κ 3 ( P,S,C ).…”