The First Triple-Decker Complex with a Carbenium Center, [CpCo(μ-C B Me )RuC Me CH ] : Synthesis, Reactivity, X-Ray Structure, and Bonding.

The first derivative of the methylium cation with the triple-decker substituent, [CpCo(C B Me )RuC Me CH ]PF (2PF ), was synthesized from the reaction of the triple-decker complex CpCo(C B Me )RuCp* (1) with the salt of the trityl cation [CPh ] . The X-ray crystal structure of 2PF reveals that the methylium carbon is bound to the ruthenium with Ru-C bond length of 2.259 Å and corresponds to the description of its structure as η -fulvene-ruthenium.

Fusion of a 1,3-diboraruthenocene to form a slipped mu-hexahydrotetraboranaphthalene triple-decker complex with two axial C--H bonds.

Colliding double deckers: Addition of zinc to a reaction mixture of [{Cp*RuCl}(4)]/pentamethyl-2,3-dihydro-1,3-diborole (C(3)B(2)Me(5)H) in THF leads to three known double- and triple-decker complexes of [C(3)B(2)Me(5)](-), and unexpectedly to the slipped triple-decker (see picture) with two fused diborole rings. The endo C--H bonds of two MeC--H groups donate two additional electrons to achieve the stable 34 VE configuration.

Diboryl and diboranyl porphyrin complexes: synthesis, structural motifs, and redox chemistry: diborenyl porphyrin or diboranyl isophlorin?

The syntheses of diboryl porphyrin complexes [(BX2)2(ttp)] (ttp: dianion of tetra-p-tolylporphyrin) and the B-B single-bond diboranyl complexes [(BX)2(ttp)] (X=F, Cl, Br, I) are given. The former are prepared from the reactions of BX3 (X=F, Cl) with [Li2(ttp)] and the latter from B(2)Cl(4) (X=Cl), the reaction of SbF3 with [(BCl)2(ttp)] (for X=F), and, in the cases of X=Br or I, in a remarkable reductive coupling reaction resulting directly from the reaction of BBr3 or BI3 with [Li2(ttp)]. Density functional theory (DFT) calculations on the thermochemical parameters for the reductive coupling reactions (and those calculated for related dipyrromethene complexes) indicate that a combination of the reducing ability of bromide and iodide ions combined with the constrained environment of the porphyrin ligand contribute to the driving force.

A "tetrameric" 3,4-di-p-tolyl-1,2,5-oxadiborole derivative.

In the title compound, 1,1,6a,7,9a,10-hexachloro-2,3,5,6,8,9,11,12-octa-p-tolyl-1,6a,9a,12a-tetraborata-3a,4a,7,10-tetrabora-4a(1),6b,9b,12b-tetraoxonia-4-oxatetracyclopenta[1,2-a:2,1,5-de:1,2-g:1,2-i]naphthalene dichloromethane pentasolvate, C(64)H(56)B(8)Cl(6)O(5).5CH(2)Cl(2), two condensed oxadiborole rings are attached to two further oxadiborole rings in a type of donor-acceptor bonding, thus forming a ten-membered alternating (B-O)(5) naphthalene-like arrangement as the central building block.

Coordinated B Bridges in Porphyrins-Unexpected Formation of a Diborane(4)- from a Diborylporphyrin.

Fitting B bridges in porphyrins can be achieved by reaction of dilithiated porphyrins with B Cl as well as by reductive elimination from diborylporphyrins. Coordination takes place under rectangular distortion of the porphyrin framework.

Blue Tetrakis(diisopropylamino)-cyclo-tetraborane and Yellow Tetrakis(tetramethylpiperidino)tetrabora-tetrahedrane.

The colored boranes closo-1 and cyclo-2 are obtained upon dehalogenation of sterically hindered diaminodichlorodiborane(4) 3. The TMP groups of 1 cause the formation of a tetrahedrane, whereas in 2 the diisopropylamino substituents stabilize the bent four-membered ring. TMP=2,2,6,6-tetramethylpiperidino.

A Boron-Bridged Tetrathiaporphyrinogen.

Lewis acid and Lewis base centers are simultaneously present in the boron-bridged thiophene-containing porphyrinogen 1 that has been synthesized in high yield. Its crystal structure reveals a nonplanar macrocycle; this and the colorless aspect suggest the absence of a delocalized π-electron system. R = NiPr .

Apically Linked Small Metallacarborane Clusters. Directed Synthesis and Structural Characterization of 7,7'-[CpCo(2,3-Et(2)C(2)B(4)H(3)](2) and [CpCo(2,3-Et(2)C(2)B(4)H(3)-7)](2)X Complexes (X = MeCH, HC=CH, C&tbd1;C)(,)(1).

A series of novel bis(cobaltacarboranyl) (CoC(2)B(4))(2)X dicluster complexes whose B(7) (apex) atoms are linked by organic moieties involving sp-, sp(2)-, or sp(3)-hybridized carbon, or by a direct B(7)-B(7') bond, has been prepared by extension of the recently described "recapitation" method (Curtis, M. A.; et al.

Electron-poor 2,3-Dihydro-1,3-Diborolyl Complexes of Iron and Ruthenium: Synthesis, Reactivity, and Crystal and Electronic Structures of an Iron Sandwich Complex.

The addition product of sodium hydride and the 2,3-dihydro-1,3-diborole (CiPr) (BEt) CHMe (3c) reacted with [{(C Me )FeCl} ] to produce the green sandwich complex [(C Me )Fe{n -(CiPr) (BEt) CMe}] (2 c), which formally contains 16 valence electrons (VE). Complex 2c has unexpected structural properties in the solid state: the 1,3-diborolyl ring is extremely folded (41°), and the Fe-C2 distance is short (1.90 Å).