Strong Closed-Shell Interactions in Inorganic Chemistry.

This critical review presents a comprehensive study of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) towards construction and synthesis of metal–organic frameworks (MOFs). We describe the geometries of 131 SBUs, their connectivity and composition. This contribution presents a comprehensive list of the wide variety of transition-metal carboxylate clusters which may serve as secondary building units (SBUs) in the construction and synthesis of metal–organic frameworks. The SBUs discussed here were obtained from a search of molecules and extended structures archived in the Cambridge Structure Database (CSD, version 5.28, January 2007) which included only crystals containing metal carboxylate linkages (241 references).

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Secondary building units, nets and bonding in the chemistry of metal–organic frameworks

The occurrence of interpenetration in metal–organic and inorganic networks has been investigated by a systematic analysis of the CSD and ICSD structural databases. For this purpose, a novel version of TOPOS (a program package for multipurpose crystallochemical analysis) has been employed, where the procedure of recognition of interpenetrating nets is based on the representation of a crystal structure as a finite reduced graph. In this paper we report a comprehensive list (301 Refcodes) of interpenetrating metal–organic 3D structures from CSD, that are analyzed on the basis of their topologies. Interesting trends and novel features have been observed and distinct classes of interpenetrating nets have been envisaged, depending on the relationships of the individual motifs.

Interpenetrating metal–organic and inorganic 3D networks: a computer-aided systematic investigation. Part I. Analysis of the Cambridge structural database

The distribution of distances from atoms of a particular element E to a probe atom X (oxygen in most cases), both bonded and intermolecular non-bonded contacts, has been analyzed. In general, the distribution is characterized by a maximum at short E⋯X distances corresponding to chemical bonds, followed by a range of unpopulated distances – the van der Waals gap – and a second maximum at longer distances – the van der Waals peak – superimposed on a random distribution function that roughly follows a d3 dependence. The analysis of more than five million interatomic “non-bonded” distances has led to the proposal of a consistent set of van der Waals radii for most naturally occurring elements, and its applicability to other element pairs has been tested for a set of more than three million data, all of them compared to over one million bond distances.

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A cartography of the van der Waals territories

Percent buried volume for phosphine and N-heterocyclic carbene ligands : steric properties in organometallic chemistry

The coordination chemistry of 2,2‘-dipyridyl diselenide (PySeSePy) (2) (C10H8N2Se2) has been investigated and its crystal structure has been determined (monoclinic, P21/c, a = 10.129(2) A, b = 5.7332(12) A, c = 19.173(3) A, β = 101.493(8)°, Z = 4). In metal complexes the ligand was found to coordinate in three different modes, as also confirmed by X-ray structure determination. N,N‘-coordination was found in the zinc complex [Zn(PySeSePy)Cl2] (3) (C10H8Cl2N2Se2Zn, triclinic, P1, a = 7.9430(10) A, b = 8.147(2) A, c = 11.999(2) A, α = 93.685(10)°, β = 107.763(10)°, γ = 115.440(10)°, Z = 2) and Se,Se‘-coordination in the adduct of the ligand with bis(pentafluorophenyl)mercury(II) [PySeSePyHg(C6F5)2] (5) (C10H8F10HgN2Se2, monoclinic, P21/n, a = 7.7325(10) A, b = 5.9974(14) A, c = 25.573, β = 98.037(10)°, Z = 2), which however displays only weak interactions between selenium and mercury. The reaction of the ligand with norbornadiene carbonyl complexes of molybdenum and tungsten leads to reductive cleavage of ...

Coordination Chemistry of 2,2‘-Dipyridyl Diselenide: X-ray Crystal Structures of PySeSePy, [Zn(PySeSePy)Cl2], [(PySeSePy)Hg(C6F5)2], [Mo(SePy)2(CO)3], [W(SePy)2(CO)3], and [Fe(SePy)2(CO)2] (PySeSePy = C5H4NSeSeC5H4N; SePy = [C5H4N(2-Se)-N,Se])

(Triphenylphosphine)(selenourea)gold(I) chloride [Ph3PAuSeC- (NH2)2]+ Cl- (1) and the corresponding dppm derivative dppm[AuSeC(NH2)2]22+ 2l- (2) are prepared from SeC- (NH2)2 and the appropriate chloro(phosphine)gold(I) complex. The reaction between 1 and aqueous Na2CO3 leads to the neutral complex μ-selenido{bis[(triphenylphosphine)gold(I)]} (Ph3PAu)2Se (3). An analogous reaction with 2 leads to a dark red oil, which has not yet been characterized. The reaction between 3, Ph3PAuCl, and AgSbF6 leads to the ionic complex [(Ph3PAu)3Se]+SbF6- (4) in good yield. X-ray structure analyses of 1,2, and 3 confirm the expected linear geometry at the gold atom and reveal short intramolecular Au – Au contacts for 2 and 3. Short nonbonding distances between the nitrogen atoms of the amino groups and the chloride ions in the crystal structures of 1 and 2 probably indicate hydrogen bonds.

Gold Complexes with Selenium Ligands, IV(1) Preparation, Crystal Structures and Reactions of Phosphine(selenourea)gold(I) Complexes

(Triphenylphosphine)phenylselenolatogold(I), Ph3PAuSePh (1), and the corresponding dppm derivative, [(dppm)(AuSePh)2] (3), are prepared from Me3SiSePh and the appropriate (phosphine)chlorogold(I) complex. The reaction between Ph3PAuCl, Ph2Se2 and AgSbF6 leads to the salt [(Ph3PAu)2SePh]+SbF−6 (2), with a bridging PhSe ligand. X-ray structure analyses of 1 and 2 confirm the expected linear geometry at gold and reveal short Au-Au contacts; both compounds may thus be regarded as loose dimers.

Gold complexes with selenium ligands, I. Preparation and crystal structures of phenylselenolato‐gold(I) complexes

Part 1: 1,3-Dipolar addition of activated alkyne towards coordinated azido group in ruthenium(II) complexes containing η5-cyclichydrocarbons

Di- and tetranuclear silver (I)-saccharinate complexes with 2-pyridineethanol and 2-pyridinepropanol: Syntheses, crystal structures, spectroscopic and thermal analyses of [Ag2(sac)2(pyet)2] and [Ag4(sac)4(pypr)2]

Carsten Thöne

Papers

Coordination Chemistry of 2,2‘-Dipyridyl Diselenide: X-ray Crystal Structures of PySeSePy, [Zn(PySeSePy)Cl2], [(PySeSePy)Hg(C6F5)2], [Mo(SePy)2(CO)3], [W(SePy)2(CO)3], and [Fe(SePy)2(CO)2] (PySeSePy = C5H4NSeSeC5H4N; SePy = [C5H4N(2-Se)-N,Se])

Gold Complexes with Selenium Ligands, IV(1) Preparation, Crystal Structures and Reactions of Phosphine(selenourea)gold(I) Complexes

Gold complexes with selenium ligands, I. Preparation and crystal structures of phenylselenolato‐gold(I) complexes

Part 1: 1,3-Dipolar addition of activated alkyne towards coordinated azido group in ruthenium(II) complexes containing η5-cyclichydrocarbons

Di- and tetranuclear silver (I)-saccharinate complexes with 2-pyridineethanol and 2-pyridinepropanol: Syntheses, crystal structures, spectroscopic and thermal analyses of [Ag2(sac)2(pyet)2] and [Ag4(sac)4(pypr)2]