Anion-Directed Solid-State Structures of Copper(I) and Silver(I) Adducts of Ruthenium Ethyne-1,2-diyl Compounds

© 2015 American Chemical Society. (Chemical Equation Presented) A number of group 11 salts, [MX] (M = Ag, X < sup > - < /sup > = < sup > - < /sup > O < inf > 3 < /inf > SCF < inf > 3 < /inf > , < sup > - < /sup > O < inf > 2 < /inf > CCF < inf > 3 < /inf > , BF < inf > 4 < /inf > < sup > - < /sup > ; M = Cu; X = Cl, Br) and [Cu(MeCN) < inf > 4 < /inf > ][PF < inf > 6 < /inf > ], were found to react in varying stoichiometries with ethyne-1,2-diyl compounds, [{Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -C=C)] (R = H, Me), to give a number of complex cations. The trication salts [Ag < inf > 3 < /inf > ({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > Me)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -? < sup > 1 < /sup > :? < sup > 1 < /sup > -C= C)) < inf > 3 < /inf > ](O < inf > 3 < /inf > SCF < inf > 3 < /inf > ) < inf > 3 < /inf > , [Ag < inf > 3 < /inf > ({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -? < sup > 1 < /sup > :? < sup > 1 < /sup > -C=C))({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -? < sup > 1 < /sup > :? < sup > 2 < /sup > -C= C)) < inf > 2 < /inf > ](BF < inf > 4 < /inf > ) < inf > 3 < /inf > , and [Cu < inf > 3 < /inf > ({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -? < sup > 1 < /sup > :? < sup > 2 < /sup > -C=C))({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -? < sup > 2 < /sup > -C=C))](PF < inf > 6 < /inf > ) < inf > 3 < /inf > result from the use of the respective anion salts in their syntheses. Coordination of Ag < sup > + < /sup > by the ethyne-1,2-diyl complexes in the presence of F < inf > 3 < /inf > CCO < inf > 2 < /inf > < sup > - < /sup > yields the tetranuclear complexes [Ag < inf > 4 < /inf > ({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -? < sup > 2 < /sup > -C=C)) < inf > 2 < /inf > ](µ < inf > 2 < /inf > -O < inf > 2 < /inf > CCF < inf > 3 < /inf > ) < inf > 4 < /inf > (R = H, Me). The reaction of CuCl does not afford the discrete dimeric complexes normally observed for internal alkynes and metal alkynyl complexes but, rather, the 1-D polymer [Cu < inf > 2 < /inf > (µ-Cl) < inf > 2 < /inf > ({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (? < sup > 2 < /sup > -C= C))] < inf > (8|8) < /inf > , while CuBr gives the discrete dimer motif known in the literature. The solution structures at 1/2, 1/1, and 2/1 stoichiometries of Ag < sup > + < /sup > /[{Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 5 < /inf > )} < inf > 2 < /inf > (µ < inf > 2 < /inf > -C=C)] have been probed spectroscopically, and the {Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} environments appear to be equivalent and, likewise, the resonances attributable to their C=C units. In a subsequent reaction of [{Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -C=C)] and AgBF < inf > 4 < /inf > use of a strict Ag < sup > + < /sup > /ethyne-1,2-diyl ratio gave [Ag({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 5 < /inf > )} < inf > 2 < /inf > (? < sup > 2 < /sup > -C=C)) < inf > 2 < /inf > ](BF < inf > 4 < /inf > ). The analogous Cu < sup > + < /sup > adduct [Cu({Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 5 < /inf > )} < inf > 2 < /inf > (? < sup > 2 < /sup > -C= C)) < inf > 2 < /inf > ](PF < inf > 6 < /inf > ) is observed, along with the tricopper(I) adduct from the reaction of [{Ru(CO) < inf > 2 < /inf > (?-C < inf > 5 < /inf > H < inf > 4 < /inf > R)} < inf > 2 < /inf > (µ < inf > 2 < /inf > -C=C)] and [Cu(NCMe) < inf > 4 < /inf > ](PF < inf > 6 < /inf > ). A combination of factors appears to control the solid-state structures of these coinage metal adducts, with the anion found to be that which influences the packing to the greatest extent

Magnetic studies of metal ion coordination clusters encapsulated with thiacalixarene

© CSIRO 2014. Three thiacalix[4]arene polynuclear complexes have been prepared by literature methods for detailed magnetic investigation. The [Fe 3 O(L) 2 ] (LH 4 = thiacalix[4]arene) complex is found to exhibit interesting anti-ferromagnetic exchange coupling. Jahn-Teller distortion in [Cu 4 (L) 2 ] complex leads to strong anti-ferromagnetic coupling at low temperatures. The temperature-dependent susceptibility of the [(µ-H 2 O)Eu 2 (LH) 2 (DMF) 4 ] complex is well described by a ground state involving the thermal population of the lowest three excited states

The structural definition of some novel adducts of stoichiometry CuX:dpex:MeCN (2:1:1)(n), X = (pseudo-) halogen, dppx = Ph2E(CH2)xEPh2, E = P, As, Sb

Single-crystal X-ray studies have defined the structures of a number of novel adducts of the form CuX:dpex (2: 1), X = (pseudo)halide, dpex = bis(diphenylpnicogeno)alkane, Ph2E(CH2)(x)EPh2, E = P, As, of diverse types, solvated with acetonitrile. CuBr:dpem (2:1)2. 2MeCN (E = both P, As) are tetranuclear, derivative of the familiar 'step' structure, while CuCl:dpph (MeCN solvate) and CuBr:dppe (MeCN solvate) yield one-dimensional polymers (i.e., x = 1, 2, 6 for dppx, x = m, e, h), as also does CuSCN:dpam (MeCN solvate). In CuI:dpsm:MeCN (3:1:2) ('dpsm' = Ph2Sb(CH2)SbPh2), CuI:dpsm (2:02 'step' units are connected into an infinite 'stair' polymer by interspersed (MeCN)CuI linkers. (c) 2005 Elsevier 13N. All rights reserved

Functionalized macrocycles from functionalized tetra-amines: Pendent-arm macrocycles derived from dichloropivalic acid

Reaction between ethane-1,2-diamine and 3,3'-dichloropivalic acid results in different, isomeric tetra-amine derivatives, one a tetraamino carboxylic acid and the other a carboxamidotriamino alcohol, depending upon reaction conditions, Intended conversion of the Cu(II) complex of the former to a cyclam-like macrocycle through reaction with nitroethane and formaldehyde results in isolation of derivatives of both the former and the latter. This can be rationalized by assuming the intermediacy of an azetidinone, a species similar to that seen in simpler reactions of dichloropivalates. A single reaction thereby provides pendent-arm macrocycles where one has an electrophilic and the other a nucleophilic substituent. Parallel chemistry is not seen in the reaction between propane-1,3-diamine and 3,3'-dichloropivalate

Mixed-metal cluster chemistry. 28. Core enlargement of tungsten-iridium clusters with alkynyl, ethyndiyl, and butadiyndiyl reagents

Copyright © 2005 American Chemical SocietyReaction of [WIr3(mu-CO)3(CO)8(eta-C5Me5)] (1c) with [W(C[triple bond]CPh)(CO)3(eta-C5H5)] afforded the edge-bridged tetrahedral cluster [W2Ir3(mu4-eta2-C2Ph)(mu-CO)(CO)9(eta-C5H5)(eta-C5Me5)] (3) and the edge-bridged trigonal-bipyramidal cluster [W3Ir3(mu4-eta2-C2Ph)(mu-eta2-C=CHPh)(Cl)(CO)8(eta-C5Me5)(eta-C5H5)2] (4) in poor to fair yield. Cluster 3 forms by insertion of [W(C[triple bond]CPh)(CO)3(eta-C5H5)] into Ir-Ir and W-Ir bonds, accompanied by a change in coordination mode from a terminally bonded alkynyl to a mu4-eta2 alkynyl ligand. Cluster 4 contains an alkynyl ligand interacting with two iridium atoms and two tungsten atoms in a mu4-eta2 fashion, as well as a vinylidene ligand bridging a W-W bond. Reaction of [WIr3(CO)11(eta-C5H5)] (1a) or 1c with [(eta-C5H5)(CO)2 Ru(C[triple bond]C)Ru(CO)2(eta-C5H5)] afforded [Ru2WIr3(mu5-eta2-C2)(mu-CO)3(CO)7(eta-C5H5)2(eta-C5R5)] [R = H (5a), Me (5c)] in low yield, a structural study of 5a revealing a WIr3 butterfly core capped and spiked by Ru atoms; the diruthenium ethyndiyl precursor has undergone Ru-C scission, with insertion of the C2 unit into a W-Ir bond of the cluster precursor. Reaction of [W2Ir2(CO)10(eta-C5H5)2] with the diruthenium ethyndiyl reagent gave [RuW2Ir2{mu4-eta2-(C2C[triple bond]C)Ru(CO)2(eta-C5H5)}(mu-CO)2(CO)6(eta-C5H5)3] (6) in low yield, a structural study of 6 revealing a butterfly W2Ir2 unit capped by a Ru(eta-C5H5) group resulting from Ru-C scission; the terminal C2 of a new ruthenium-bound butadiyndiyl ligand has been inserted into the W-Ir bond. Reaction between 1a, [WIr3(CO)11(eta-C5H4Me)] (1b), or 1c and [(eta-C5H5)(CO)3W(C[triple bond]CC[triple bond]C)W(CO)3(eta-C5H5)] afforded [W2Ir3{mu4-eta2-(C2C[triple bond]C)W(CO)3(eta-C5H5)}(mu-CO)2(CO)2(eta-C5H5)(eta-C5R5)] [R = H (7a), Me (7c); R5 = H4Me (7b)] in good yield, a structural study of 7c revealing it to be a metallaethynyl analogue of 3.Gulliver T. Dalton, Lydie Viau, Susan M. Waterman, Mark G. Humphrey, Michael I. Bruce, Paul J. Low, Rachel L. Roberts, Anthony C. Willis, George A. Koutsantonis, Brian W. Skelton, and Allan H. Whit

Domino Reactions for the Synthesis of Anthrapyran-2-ones and the Total Synthesis of the Natural Product (±)-BE-26554A

A domino alkyne addition/CO insertion/Nu acylation reaction to a series of novel anthrapyran-2-ones in good to excellent yields is described. In addition, an efficient synthetic sequence involving carbonylation, formation of a β-keto-sulfoxide, and cyclization is presented en route to the antibiotic and antitumor compound (±)-BE-26554A

Domino Reactions for the Synthesis of Anthrapyran-2-ones and the Total Synthesis of the Natural Product (±)-BE-26554A

A domino alkyne addition/CO insertion/Nu acylation reaction to a series of novel anthrapyran-2-ones in good to excellent yields is described. In addition, an efficient synthetic sequence involving carbonylation, formation of a β-keto-sulfoxide, and cyclization is presented en route to the antibiotic and antitumor compound (±)-BE-26554A