Dipyrromethane-Based PGeP Pincer Germyl Rhodium Complexes

A family of germyl rhodium complexes derived from the PGeP germylene 2,2’-bis(di-isopropylphosphanylmethyl)-5,5’-dimethyldipyrromethane-1,1’-diylgermanium(II), Ge(pyrmPⁱPr₂)₂CMe₂ ( 1 ), has been prepared. Germylene 1 reacted readily with [RhCl(PPh₃)₃] and [RhCl(cod)(PPh₃)] (cod=1,5-cyclooctadiene) to give, in both cases, the PGeP-pincer chloridogermyl rhodium(I) derivative [Rh{κ³P,Ge,P-GeCl(pyrmPⁱPr₂)₂CMe₂}(PPh₃)] ( 2 ). Similarly, the reaction of 1 with [RhCl(cod)(MeCN)] afforded [Rh{κ³P,Ge,P-GeCl(pyrmPⁱPr₂)₂CMe₂}(MeCN)] ( 3 ). The methoxidogermyl and methylgermyl rhodium(I) complexes [Rh{κ³P,Ge,P-GeR(pyrmPⁱPr₂)₂CMe₂}(PPh₃)] (R=OMe, 4 ; Me, 5 ) were prepared by treating complex 2 with LiOMe and LiMe, respectively. Complex 5 readily reacted with CO to give the carbonyl rhodium(I) derivative [Rh{κ³P,Ge,P-GeR(pyrmPⁱPr₂)₂CMe₂}(CO)] ( 6 ), with HCl, HSnPh₃ and Ph₂S₂ rendering the pentacoordinate methylgermyl rhodium(III) complexes [RhHX{κ³P,Ge,P-GeMe(pyrmPⁱPr₂)₂CMe₂}] (X=Cl, 7 ; SnPh₃, 8 ) and [Rh(SPh)₂{κ³P,Ge,P-GeMe(pyrmPⁱPr₂)₂CMe₂}] ( 9 ), respectively, and with H₂ to give the hexacoordinate derivative [RhH₂{κ³P,Ge,P-GeMe(pyrmPⁱPr₂)₂CMe₂}(PPh₃)] ( 10 ). Complexes 3 and 5 are catalyst precursors for the hydroboration of styrene, 4-vinyltoluene and 4-vinylfluorobenzene with catecholborane under mild conditions.     

Pincer‐Type Heck Catalysts and Mechanisms Based on PdIV Intermediates: A Computational Study

Pincer‐type palladium complexes are among the most active Heck catalysts. Due to their exceptionally high thermal stability and the fact that they contain Pd^II centers, controversial Pd^II/Pd^IV cycles have been often proposed as potential catalytic mechanisms. However, pincer‐type Pd^IV intermediates have never been experimentally observed, and computational studies to support the proposed Pd^II/Pd^IV mechanisms with pincer‐type catalysts have never been carried out. In this computational study the feasibility of potential catalytic cycles involving Pd^IV intermediates was explored. Density functional calculations were performed on experimentally applied aminophosphine‐, phosphine‐, and phosphite‐based pincer‐type Heck catalysts with styrene and phenyl bromide as substrates and (E)‐stilbene as coupling product. The potential‐energy surfaces were calculated in dimethylformamide (DMF) as solvent and demonstrate that Pd^II/Pd^IV mechanisms are thermally accessible and thus a true alternative to formation of palladium nanoparticles. Initial reaction steps of the lowest energy path of the catalytic cycle of the Heck reaction include dissociation of the chloride ligands from the neutral pincer complexes [{2,6‐C₆H₃(XPR₂)₂}Pd(Cl)] [X=NH, R=piperidinyl ( 1 a ); X=O, R=piperidinyl ( 1 b ); X=O, R=iPr ( 1 c ); X=CH₂, R=iPr ( 1 d )] to yield cationic, three‐coordinate, T‐shaped 14e^? palladium intermediates of type [{2,6‐C₆H₃(XPR₂)₂}Pd]⁺ ( 2 ). An alternative reaction path to generate complexes of type 2 (relevant for electron‐poor pincer complexes) includes initial coordination of styrene to 1 to yield styrene adducts [{2,6‐C₆H₃(XPR₂)₂}Pd(Cl)(CH₂?CHPh)] ( 4 ) and consecutive dissociation of the chloride ligand to yield cationic square‐planar styrene complexes [{2,6‐C₆H₃(XPR₂)₂}Pd(CH₂?CHPh)]⁺ ( 6 ) and styrene. Cationic styrene adducts of type 6 were additionally found to be the resting states of the catalytic reaction. However, oxidative addition of phenyl bromide to 2 result in pentacoordinate Pd^IV complexes of type [{2,6‐C₆H₃(XPR₂)₂}Pd(Br)(C₆H₅)]⁺ ( 11 ), which subsequently coordinate styrene (in trans position relative to the phenyl unit of the pincer cores) to yield hexacoordinate phenyl styrene complexes [{2,6‐C₆H₃(XPR₂)₂}Pd(Br)(C₆H₅)(CH₂?CHPh)]⁺ ( 12 ). Migration of the phenyl ligand to the olefinic bond gives cationic, pentacoordinate phenylethenyl complexes [{2,6‐C₆H₃(XPR₂)₂}Pd(Br)(CHPhCH₂Ph)]⁺ ( 13 ). Subsequent β‐hydride elimination induces direct HBr liberation to yield cationic, square‐planar (E)‐stilbene complexes with general formula [{2,6‐C₆H₃(XPR₂)₂}Pd(CHPh?CHPh)]⁺ ( 14 ). Subsequent liberation of (E)‐stilbene closes the catalytic cycle.     

Chiral Pt(II)/Pd(II) pincer complexes that show C-H?Cl hydrogen bonding: Synthesis and applications to catalytic asymmetric aldol and silylcyanation reactions

A chiral C₂-symmetric NCN ligand, (5R,7R)-1,3-bis(6,6-dimethyl-5,6,7,8-tetrahydro-5,7-methanoquinolin-2-yl)benzene has been synthesized. A direct cyclometalation of this ligand with K₂MCl₄ (M = Pt, Pd) in dry acetic acid offered the corresponding pincer complexes, [(5R,7R)-1,3-bis(6,6-dimethyl-5,6,7,8-tetrahydro-5,7-methanoquinolin-2-yl)phenyl]platinum(II) chloride 5a and its palladium(II) analogue 5b. The Pt(II) and Pd(II) complexes 5 were characterized by NMR spectroscopy, and X-ray crystal structure analysis was done for the Pt(II) complex. The NMR data for both the complexes and X-ray crystal structural data for the chloro-Pt(II) complex indicate the existence of intramolecular C-H?Cl hydrogen bonding both in solution and in solid states. Chloride abstraction from 5a by treatment with silver triflate resulted in the corresponding triflate complex 6a, which generates the corresponding cationic aqua complex 7a in the presence of water molecules. The Pt(II) complex 6a/7a was used as asymmetric catalyst in the aldol reaction between methyl isocyanoacetate and aldehydes and also in the silylcyanation of aldehydes.     

Unsymmetrical, oxazolinyl-containing achiral and chiral NCN pincer ligand precursors and their complexes with palladium(II)

The unsymmetrical, achiral and chiral NCN pincer ligand precursors (3a-3d) with oxazoline and pyrazole as N donors as well as (3e) which has oxazolinyl and amino group have been synthesized in a facile manner in four steps starting from commercially available isophthalaldehyde. Direct C2 metallation of the precursors (3a-3e) with Pd(OAc)₂ in refluxing HOAc, followed by treatment with LiCl at room temperature provided convenient access to the corresponding pincer palladium(II) complexes (4a-4e). The molecular structure of complex 4e has been determined by X-ray single-crystal diffraction. The obtained Pd complexes exhibited good activities in the Suzuki reactions of aryl bromides and activated aryl chlorides with phenylboronic acid.     

Dehydrogenation of amine–boranes catalyzed by a PCsp3P pincer iridium complex

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A Redox-Active Tetrazine-Based Pincer Ligand for the Reduction of N-Oxyanions Using a Redox-Inert Metal

The reaction chemistry of the bis-tetrazinyl pyridine ligand (btzp) towards nitrogen oxyanions coordinated to zinc is studied in order to explore the reduction of the NO_x⁻ substrates with a redox-active ligand in the absence of redox activity at the metal. Following syntheses and characterization of (btzp)ZnX₂ for X=Cl, NO₃ and NO₂, featuring O−Zn linkage of both nitrogen oxyanions, it is shown that a silylating agent selectively delivers silyl substituents to tetrazine nitrogens, without reductive deoxygenation of NO_x⁻¹. A new synthesis of the highly hydrogenated H₄btzp, containing two dihydrotetrazine reductants is described as is the synthesis and characterization of (H₄btzp)ZnX₂ for X=Cl and NO₃, both of which show considerable hydrogen bonding potential of the dihydrotetrazine ring NH groups. The (H₄btzp)ZnCl₂ complex does not bind zinc in the pincer pocket, but instead H₄btzp becomes a bridge between neighboring atoms through tetrazine nitrogen atoms, forming a polymeric chain. The reaction of AgNO₂ with (H₄btzp)ZnCl₂ is shown to proceed with fast nitrite deoxygenation, yielding water and free NO. Half of the H₄btzp reducing equivalents form Ag⁰ and thus the chloride ligand remains coordinated to the zinc metal center to yield (btzp)ZnCl₂. To compare with AgNO₂, experiments of (H₄btzp)ZnCl₂ with NaNO₂ result in salt metathesis between chloride and nitrite, highlighting the importance of a redox-active cation in the reduction of nitrite to NO.