Binding H2, N2, H-, and BH3 to transition-metal sulfur sites: synthesis and properties of [RuL(PR3)(N2Me2S2)] Complexes (L=eta2-H2, H-, BH3; R=Cy, iPr)

The reactions of [Ru(N₂)(PR₃)(‘N₂Me₂S₂’)] [‘N₂Me₂S₂’=1,2‐ethanediamine‐N,N′‐dimethyl‐N,N′‐bis(2‐benzenethiolate)(2?)] [ 1 a (R=iPr), 1 b (R=Cy)] and [μ‐N₂{Ru(N₂)(PiPr₃)(‘N₂Me₂S₂’)}₂] ( 1 c ) with H₂, NaBH₄, and NBu₄BH₄, intended to reduce the N₂ ligands, led to substitution of N₂ and formation of the new complexes [Ru(H₂)(PR₃)(‘N₂Me₂S₂’)] [ 2 a (R=iPr), 2 b (R=Cy)], [Ru(BH₃)(PR₃)(‘N₂Me₂S₂’)] [ 3 a (R=iPr), 3 b (R=Cy)], and [Ru(H)(PR₃)(‘N₂Me₂S₂’)]^? [ 4 a (R=iPr), 4 b (R=Cy)]. The BH₃ and hydride complexes 3 a , 3 b , 4 a , and 4 b were obtained subsequently by rational synthesis from 1 a or 1 b and BH₃?THF or LiBEt₃H. The primary step in all reactions probably is the dissociation of N₂ from the N₂ complexes to give coordinatively unsaturated [Ru(PR₃)(‘N₂Me₂S₂’)] fragments that add H₂, BH₄^?, BH₃, or H^?. All complexes were completely characterized by elemental analysis and common spectroscopic methods. The molecular structures of [Ru(H₂)(PR₃)(‘N₂Me₂S₂’)] [ 2 a (R=iPr), 2 b (R=Cy)], [Ru(BH₃)(PiPr₃)(‘N₂Me₂S₂’)] ( 3 a ), [Li(THF)₂][Ru(H)(PiPr₃)(‘N₂Me₂S₂’)] ([Li(THF)₂]‐ 4 a ), and NBu₄[Ru(H)(PCy₃)(‘N₂Me₂S₂’)] (NBu₄‐ 4 b ) were determined by X‐ray crystal structure analysis. Measurements of the NMR relaxation time T₁ corroborated the η² bonding mode of the H₂ ligands in 2 a (T₁=35 ms) and 2 b (T₁=21 ms). The H,D coupling constants of the analogous HD complexes HD‐ 2 a (¹J(H,D)=26.0 Hz) and HD‐ 2 b (¹J(H,D)=25.9 Hz) enabled calculation of the H? D distances, which agreed with the values found by X‐ray crystal structure analysis ( 2 a : 92 pm (X‐ray) versus 98 pm (calculated), 2 b : 99 versus 98 pm). The BH₃ entities in 3 a and 3 b bind to one thiolate donor of the [Ru(PR₃)(‘N₂Me₂S₂’)] fragment and through a B‐H‐Ru bond to the Ru center. The hydride complex anions 4 a and 4 b are extremely Brønsted basic and are instantanously protonated to give the η²‐H₂ complexes 2 a and 2 b .     

1,3-dialkyl- and 1,3-diaryl-3,4,5,6-tetrahydropyrimidin-2-ylidene rhodium(i) and palladium(II) complexes: synthesis, structure, and reactivity

The synthesis of novel 1,3-diaryl- and 1,3-dialkylpyrimidin-2-ylidene-based N-heterocyclic carbenes (NHCs) and their rhodium(i) and palladium(II) complexes is described. The rhodium compounds bromo(cod)[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (7), bromo(cod)(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (8) (cod=eta(4)-1,5-cyclooctadiene, mesityl=2,4,6-trimethylphenyl), chloro(cod)(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (9), and chloro(cod)[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (10) were prepared by reaction of [[Rh(cod)Cl](2)] with lithium tert-butoxide followed by addition of 1,3-dimesityl-3,4,5,6-tetrahydropyrimidinium bromide (3), 1,3-dimesityl-3,4,5,6-tetrahydropyrimidinium tetrafluoroborate (4), 1,3-di-2-propyl-3,4,5,6-tetrahydropyrimidinium bromide (6), and 1,3-di-2-propyl-3,4,5,6-tetrahydropyrimidinium tetrafluoroborate, respectively. Complex 7 crystallizes in the monoclinic space group P2(1)/n, and 8 in the monoclinic space group P2(1). Complexes 9 and 10 were used for the synthesis of the corresponding dicarbonyl complexes dicarbonylchloro(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (11), and dicarbonylchloro[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (12). The wavenumbers nu(CO I)/nu(CO II) for 11 and 12 were used as a quantitative measure for the basicity of the NHC ligand. The values of 2062/1976 and 2063/1982 cm(-1), respectively, indicate that the new NHCs are among the most basic cyclic ligands reported so far. Compounds 3 and 6 were additionally converted to the corresponding cationic silver(i) bis-NHC complexes [Ag(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2)]AgBr(2) (13) and [Ag[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene](2)]AgBr(2) (14), which were subsequently used in transmetalation reactions for the synthesis of the corresponding palladium(II) complexes Pd(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2) (2+)(Ag(2)Br(2)Cl(4) (4-))(1/2) (15) and Pd[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2)]Cl(2) (16). Complex 15 crystallizes in the monoclinic space group P2(1)/c, and 16 in the monoclinic space group C(2)/c. The catalytic activity of 15 and 16 in Heck-type reactions was studied in detail. Both compounds are highly active in the coupling of aliphatic and aromatic vinyl compounds with aryl bromides and chlorides with turnover numbers (TONs) up to 2000000. Stabilities of 15 and 16 under Heck-couplings conditions were correlated with their molecular structure. Finally, selected kinetic data for these couplings are presented.     

高氯酸二水邻菲咯啉合铜配合物的合成和晶体结构

Crystal structure of the title compound， Cu(phen)(H₂O)₂·ClO₄(phen=1，10-phenanthroline)， was deter-mined by X-ray crystallography. It crystallizes in the monoclinic system， space group C2/c with lattice parameters a=1.49071(4)nm， b=1.38594(4)nm， c=0.70292(1)nm， β=108.509(1)° and Z=4; The Cu(Ⅰ) ion is chelated by a phen ligand and two aqua ligands in cis arrangement and assumes a C2 symmetric square-planar geometry with the CuN₂O₂ core. Eight Cu(phen)(H₂O)₂·ClO₄ molecules are interconnected by strong hydrogen bonds between coordinated water molecules and uncoordinated perchlorate anions to form a molecular scale cavities along c axis. The bond distances of Cu-N and Cu-O are 0.2003(4)nm and 0.1973(3)nm， respectively. CCDC： 197600.     

Phosphonio‐benzophospholide Zwitterions as Bridging 8e‐Donor Ligands: Synthetic and Mechanistic Studies

Reactions of the phosphonio‐benzophospholide π‐complexes 3a, b[Cr] with [M(CO)₅(olefin)] or of the σ‐complexes 2a, b[M] (M = Cr, Mo, W) with [M(CO)₃(aren)] lead to the first binuclear complexes 4a, b[CrM] featuring phosphonoio‐benzophospholides as μ‐bridging 8e‐donor ligands to two group 6 metal atoms. The constitution of the products was determined by spectroscopic and X‐ray diffraction studies. Mixed complexes with both group 6 and 7 metals were not accessible. Mechanistic studies showed that the reactions follow a complicated mechanism whose single steps may involve transfer of either M(CO)_n fragments or single CO ligands between complexes; the latter are associated with a σ/π‐coordination isomerization of the benzophospholide unit. Competition between both reaction channels can lead to the formation of product mixtures whose composition is controlled by the relative thermodynamic stabilities of the products. Computational studies suggest that in the more stable isomer of heterobimetallic complexes 4a, b[MM′] end‐on coordination to the heavier and side‐on coordination to the lighter metal atom is preferred.     

Energy transfer in solution of lanthanide complexes

The lanthanides with their well-defined energy levels provide an excellent basis to study different Ln(III)-specific energy transfer processes in a variety of chemical environments. The studies concerning intramolecular and intermolecular energy transfer processes with participation of Ln(III) ions and a variety of ligand groups in solution are reviewed. Phenomena of energy transfer from ligands to Ln(III) ions, resulting consequently in a great enhancement of the Ln(III) ion luminescence (ligand sensitized luminescence), as well as from Ln(III) to other species and between Ln(III) ions are presented.     

Dinuclear and Mononuclear Platinum(II) and Palladium(II) Complexes with Modified 2,2′‐Dipyridylamine Ligands Featuring a Cisplatin Analogous Structure Motif

In modern cancer therapy the clinical application of platinum‐based drugs is more and more limited by the occurrence of intrinsic or acquired resistances. In this context the potential use of dinuclear platinum complexes in chemotherapy is increasingly relevant. The novel complexes Pd(Bzdpa)Cl₂, Pd₂(C₄H₈(dpa)₂)Cl₄, and Pt₂(C₄H₈(dpa)₂)Cl₄ allow a direct comparison of mono‐ and dinuclear palladium and platinum complexes respectively deriving from a 2,2′‐dipyridylamine (Hdpa) ligand system. They were characterized by single crystal X‐ray analysis as well as infrared spectroscopy and elemental analysis. The cisplatin analogous mononuclear palladium complex Pd(Bzdpa)Cl₂ ( 1 ) (Bzdpa: (2,2′‐dipyridylbenzyl)amine) belongs to a range of 2,2′‐dipyridylamine‐based compounds which were extensively studied in our laboratories. 1 crystallizes in the orthorhombic space group Pna2₁ with a = 13.722(3), b = 13.457(3), c = 9.483(2), V = 1751.1(6) ų, and Z = 4. The metal binding motif of 1 was expanded by a flexible butyl‐linker to form the tetradentate C₄H₈(dpa)₂ ligand. The resulting isotypic dinuclear complexes Pd₂(C₄H₈(dpa)₂)Cl₄·2CH₃CN ( 2 ) and Pt₂(C₄H₈(dpa)₂)Cl₄·2CH₃CN ( 3 ) crystallize in the triclinic space group with a = 7.8427(2), b = 8.7940(2), c = 11.7645 (3), α = 79.219(2)°, β = 84.033(2)°, γ = 87.744(2)°, V = 792.58(3) ų ( 2 ) and a = 7.831(5), b = 8.814(5), c = 11.817(5), α = 79.271(5)°, β = 83.571(5)°, γ = 88.063(5)°, V = 796.3(8) ų ( 3 ), both with one centrosymmetrical molecule in the unit cell.     

Application of chiral thiazolidine ligands to asymmetric hydrosilation

Seven chiral thiazolidines bound rhodium complexes were synthesized and their catalytic asymmetric hydrosilation properties were investigated It was found through investigation that the configuration of newly formed chiral centre C2 of substituted chiral thiazolidines prepared from L-cysteine or its esters has no effect on the final results of catalytic asymmetric hydrosilation.The direct reason for causing this phenomenon is reported by the present quantitative results for the first time:the rapid racemation of chiral center C2 of chiral thiazolidine ligands takes place under the catalysis of rhodium(Ⅰ) complex [Rh(COD)CI]2     

对称性和配合物的构型——Ⅱ.混合配体配合物

从库仑定律出发,采用最优化法,计算了MLaL_b′型配合物各种几何异构体的几何构型稳定化能。在计算中考虑了配体L、L′的相对电荷。 计算结果表明,对称性是决定构型的首要因素。具体构型与配体的相对电荷有关。 在若干配合物中,中心原子的dⁿ构型决定其构型的骨架。 配体对构型的作用也应予考虑。对共价性程度大的配合物,应考虑轨道重叠对构型的影响。