The development in the field of coordination polymers or metal-organic coordination networks, MOCNs (metal-organic frameworks, MOFs) is assessed in terms of property investigations in the areas of catalysis, chirality, conductivity, luminescence, magnetism, spin-transition (spin-crossover), non-linear optics (NLO) and porosity or zeolitic behavior upon which potential applications could be based.

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Engineering coordination polymers towards applications

The chemistry of heterocyclic carbenes has experienced a rapid development over the last years. In addition to the imidazolin-2-ylidenes, a large number of cyclic diaminocarbenes with different ring sizes have been described. Aside from diaminocarbenes, P-heterocyclic carbenes, and derivatives with only one, or even no heteroatom within the carbene ring are known. New methods for the synthesis of complexes with N-heterocyclic carbene ligands such as the oxidative addition or the metal atom template controlled cyclization of β-functionalized isocyanides have been developed recently. This review summarizes the new developments regarding the synthesis of N-heterocyclic carbenes and their metal complexes.

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

4.2.8. Reductive Coupling 3109 5. Reaction of Aromatic Compounds 3110 5.1. Electrophilic Substitutions 3110 5.2. Radical Substitution 3111 5.3. Oxidative Coupling 3111 5.4. Photochemical Reactions 3111 6. Reaction of Carbonyl Compounds 3111 6.1. Nucleophilic Additions 3111 6.1.1. Allylation 3111 6.1.2. Propargylation 3120 6.1.3. Benzylation 3121 6.1.4. Arylation/Vinylation 3121 6.1.5. Alkynylation 3121 6.1.6. Alkylation 3121 6.1.7. Reformatsky-Type Reaction 3122 6.1.8. Direct Aldol Reaction 3122 6.1.9. Mukaiyama Aldol Reaction 3124 6.1.10. Hydrogen Cyanide Addition 3125 6.2. Pinacol Coupling 3126 6.3. Wittig Reactions 3126 7. Reaction of R,â-Unsaturated Carbonyl Compounds 3127

Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade Update

Triazoles and tetrazoles: Prime ligands to generate remarkable coordination materials

Stereoelectronic parameters associated with N-heterocyclic carbene (NHC) ligands: A quest for understanding

Reactions of naphthaleneeuropium and naphthaleneytterbium, C10H8Ln(DME) (Ln = Eu or Yb), with phenylacetylene are accompanied by the formation of the C-C bond and yield the complexes of composition Ph2C4H2Ln(DME)2. Hydrolysis of the Ph2C4H2Ln(DME)2 complexes affords a mixture of isomers of 1,4-diphenyl-1,3-butadiene. Reactions of C10H8[LnI(DME)2]2 with PhC≡CH yield mixed iodine-ethynyl complexes [ILn(μ-C≡CPh)(DME)2]2. According to the data of X-ray diffraction analysis, the ytterbium complex consists of two YbI(DME)2 units bonded through two bridging C≡CPh groups. The crystals of this complex belong to the space groupP21/c. The central cyclic Yb-C-Yb-C fragment is planar; the C(I)-Yb(I)-C(I′) angle is 86.4(3)°. The Yb-C bond lengths are 2.584(8) and 2.603(9) A.

The reactions of phenylacetylene with naphthalene complexes of europium and ytterbium. Molecular structure of [IYbC≡CPh(DME)2]2

Me2Cp′SiCl (1) (Cp′ = C5HMe4) reagiert mit Magnesium und R2PCl (R = Ph, tBu) bzw, PCl3 in Tetrahydrofuran unter Bildung von Me2Cp′SiPPh2 (4) und Me2Cp′SiPtBu2 (5) bzw. (Me2Cp′Si)3P (6). Durch Umsetzung von Me3SiPPh2 (7) oder Me3SiPC4H4Me2 (10) mit Me2Cp′GeCl (2) und Me2Cp′SnCl (3) wurden Me2Cp′EPPh2 (E = Ge (8), Sn (9)) bzw. Me2Cp′EPC4H4Me2 (E = Ge (11), Sn (12)) erhalten. 11 reagiert mit Fe(CO)5 unter Bildung von Fe(CO)4[(PC4H4Me2)GeCp′Me2] (13). 3 kristallisiert in der Raumgruppe P21/n mit a = 986,7(1), b = 1247,3(2), c = 1028,2(1) pm, β = 92,71(1)°, Z = 4 und V = 1264,1(2) 10−30 m3 (R1 = 0,0249 fur 2097 beobachtete Reflexe mit Fo ≥ 4σ(Fo). 13 kristallisiert in der Raumgruppe P21/n mit a = 967,7(3), b = 1298,70(16), c = 1832,7(3) pm, β = 95,810(19)°, Z = 4 und V = 2291,4(8) 10−30 m3 (R1 = 0,0444 fur 4043 beobachtete Reflexe mit Fo ≤ 4σ(Fo). 13 ist trigonal bipyramidal mit dem Phosphanliganden 11 in axialer Position.



Dimethyl(tetramethylcyclopentadienyl)silyl-, -germyl-, and -stannylphosphanes. X-Ray Structures of Chloro(dimethyl)tetramethylcyclopentadienyl-stannane and Tetracarbonyl[1-dimethyl(tetramethylcyclopentadienyl)germyl-3,4-dimethyl-phospholene]iron(0)



Me2Cp′SiCl (1) (Cp′ = C5HMe4) reacts with magnesium and R2PCl (R = Ph, tBu) as well as PCl3 in tetrahydrofurane yielding Me2Cp′SiPPh2 (4), Me2Cp′SiPtBu2 (5) and (Me2Cp′Si)3P (6) respectively. The reaction of Me3SiPPh2 (7) or Me3SiPC4H4Me2 (10) with Me2Cp′GeCl (2) and Me2Cp′SnCl (3) leads to the formation of Me2Cp′EPPh2 (E = Ge (8), Sn (9)) and Me2Cp′EPC4H4Me2 (E = Ge (11), Sn (12)). 11 reacts with Fe(CO)5 with formation of Fe(CO)4[(PC4H4Me2)GeCp′Me2] (13). 3 crystallizes in the space group P21/n with a = 986,7(1), b = 1247,3(2), c = 1028,2(1) pm, β = 92,71(1)°, Z = 4 and V = 1264,1(2) 10−30 m3. The final refinement resulted in R1 = 0,0249 for 2097 observed reflexions with Fo ≥ 4σ(Fo). 13 crystallizes in the space group P21/n with a = 967,7(3), b = 1298,70(16), c = 1832,7(3) pm, β = 95,810(19)°, Z = 4 and V = 2291,4(8) 10−30 m3 (R1 = 0,0444 for 4043 observed reflexions with Fo ≥ 4σ(Fo). 13 forms a trigonal bipyramide with the phosphane ligand 11 in an axial position.

Dimethyl(tetramethylcyclopentadienyl)silyl-, -germyl- und -stannyl-phosphane. Röntgenstrukturanalyse von Chloro(dimethyl)tetramethylcyclopentadienylstannan und Tetracarbonyl[1-dimethyl-(tetramethylcyclopentadienyl)germyl-3,4-dimethylphospholen]eisen(0)†

An efficient synthetic procedure for the preparation of versatile functionally substituted arylphosphines from commercially available starting materials is reported together with alternative synthetic routes for (carboxyphenyl)diphenyl phos-phines.

A New Synthesis of Hydrophilic Carboxylated Arylphosphines.

Whereas the reaction of [Rh(CO) 2 (μ-pz)] 2 (where pz is either a pyrazolato or 3,5-dimethylpyrazolato group) with 3-(diphenylphosphino)benzoic acid and (2-formylphenyl) diphenylphosphine gives the dinuclearic complexes [Rh(CO)(Ph 2 P-3-C 6 H 4 COOH)(μ- pz)] 2 ( 1 and 2 ) and [Rh(CO)(Ph 2 P-2-C 6 H 4 CHO)(μ-pz)] 2 ( 5 and 6 ) respectively, 2-(diphenylphosphino)benzoic acid gives the monorhodium compounds R h(CO)(H-pz)(Ph 2 P-2-C 6 H 4 COO ) ( 3 and 4 ). The structures of Rh(CO) ( NCHCHCHN H)(Ph 2 P-2-C 6 H 4 COO) ( 3 ) and [Rh(CO)(Ph 2 P-2-C 6 H 4 CHO)(μ- NCMeCHCMeN )] 2 ( 6 ) have been determined by X-ray diffraction analyses. Both, the monorhodium and the dirhodium complexes catalyse the hydroformylation of acyclic and cyclic olefins at 120°C and at CO and H 2 pressures of 28 atm. At 70–90°C the dinuclear complexes with 3-(diphenylphosphino)benzoic acid moieties are substantially more active than the monorhodium compounds.

Holger Hemling

Papers

The reactions of phenylacetylene with naphthalene complexes of europium and ytterbium. Molecular structure of [IYbC≡CPh(DME)2]2

Dimethyl(tetramethylcyclopentadienyl)silyl-, -germyl- und -stannyl-phosphane. Röntgenstrukturanalyse von Chloro(dimethyl)tetramethylcyclopentadienylstannan und Tetracarbonyl[1-dimethyl-(tetramethylcyclopentadienyl)germyl-3,4-dimethylphospholen]eisen(0)†

A New Synthesis of Hydrophilic Carboxylated Arylphosphines.

Effects of Changes in the Ligands on the Skeleton and the Catalytic Activity of Some New Rhodium Complexes with Pyrazolato Moieties.

A Novel Convenient Synthesis of Arylphosphines Containing Reactive Functional Groups.