324775-26-0Relevant academic research and scientific papers
Syntheses of gold-manganese and gold-rhenium clusters, and + (M = Mn, Re), and the crystal structure of BF4
Nicholson, Brian K.,Bruce, Michael I.,Shawkataly, Omar bin,Tiekink, Edward R. T.
, p. 411 - 418 (1992)
The specific additions of one, three or four Ph3PAu groups to - (M = Mn, Re) are described.Thus - in THF reacts with BF4 to give BF4.An X-ray crystal structure of the M = Mn example shows the cation to have a trigonal bipyramidal Au4Mn core with the Mn in an equatorial site.The previously known neutral (Ph3PAu)3M(CO)4 clusters are formed by addition of two Ph3PAu groups, using the mixed reagent BF4/, to Ph3PAuM(CO)5, which itself is readily prepared from - and Ph3PAuCl.
Syntheses and structures of the heterometallic clusters [(Ph 3PAu)3Re(CO)4], [(Ph3PAu) 4Re(CO)4]+, [(Ph3PAu) 6AuRe2(CO)8]+, and [(Ph 3PAu)6Re(CO)3]+
Pivoriunas,Richter,Str?hle
, p. 4301 - 4306 (2008/10/09)
The reaction of [HRe3(CO)12]2- with an excess of Ph3PAuCl in CH2Cl2 yields [(Ph 3PAu)4Re(CO)4]+ as the main product, which crystallizes as [(Ph3PAu)4Re(CO) 4]PF6·CH2Cl2 (1·CH2Cl2) after the addition of KPF 6.The crystal structure determination reveals a trigonal bipyramidal Au4Re cluster with the Re atom in equatorial position. If [(Ph 3PAu)4Re(CO)4]+ is reacted with PPh4Cl, a cation [Ph3PAu]+ is eliminated as Ph3PAuCl, and the neutral cluster [(Ph3PAu) 3Re(CO)4] (2) is formed.It combines with excess [(Ph 3PAu)4Re(CO)4]+ to afford the cluster cation, [(Ph3PAu)6AuRe2(CO) 8]+. It crystallizes from CH2Cl2 as[(Ph3PAu)6AuRe2(CO)8]PF 6·4CH2Cl2 (3·4CH 2Cl2). In [(Ph3PAu)3Re(CO) 4] the metal atoms are arranged in form of a lozenge while in [(Ph3PAu)6AuRe2(CO)8]+ two Au4Re trigonal bipyramids are connected by a common axial Au atom. The treatment of [(Ph3PAu)4Re(CO)4] + with KOH and Ph3PAuCl in methanol yields the cluster cation [(Ph3PAu)6Re(CO)3]+, which crystallizes with PF6- from CH2Cl2 as [(Ph 3PAu)6Re(CO)3]PF6·CH 2Cl2 (4·CH2Cl2). The metal atoms in this cluster form a pentagonal bipyramid with the Re atom in the axial position.
Synthesis and crystal structure of (Ph3PAu)4[AuMn(CO)5]2 and (Ph3PAu)3Re(CO)4
Richter, Markus,Fenske, Dieter,Str?hle, Joachim
, p. 907 - 912 (2007/10/03)
The reaction of [Mn(CO)5]macr; with the cluster cation [(Ph3PAu)8]2+ in thf yields the heterometallic cluster [(Ph3PAu)4 [AuMn(CO)5]2 (1) as the main product besides small amounts of (Ph3PAu)3Mn(CO)4. The former crystallizes as 1-thf in form of red blocks in the triclimc space group P1? with a = 1391.0(1), b = 1426.7(1), c = 2308.3(2) pm, a = 92.87(1), β = 97.54(1), γ = 96.43(1 )° and Z = 2. The inner Au6 skeleton of the almost centrosymmetrical cluster consists of two Au4 tetrahedra sharing one edge. Two gold atoms bind a Mn(CO)5 fragment, whereas to the other four gold atoms phosphine ligands are coordinated. The Au-Au distances range from 263.2(1) to 281.9(1) pm, and the Au-Mn distances are 256.6(3) and 256.9(2) pm. By the reaction of [(Ph3PAu)8]2+ with [Re2(CO)9]2- the cluster (Ph3PAu)3Re(CO)4 (2) is obtained in low yield besides the homometallic cluster [(AuPPh3)7]+ as the main product. 2 crystallizes from toluene as 2·C7H8 in the form of yellow blocks with the orthorhombic space group Pna21, and a = 1758.7(3), b = 1648.7(5), c = 2049.3(5) pm. The four metal atoms form a planar lozenge with the Re atom in equatorial position. The Re-Au distances range from 271.2(1) to 273.7(1) pm, and the Au-Au distances are 278.2(1) and 278.4(1) pm.
Reactions of Trisodium Tetracarbonylmetalates(3-) of Manganese and Rhenium with Broensted Acids and Other Electrophiles. Synthesis of H2M(CO)4- (M=Mn and Re), (CH3)2Re(CO)4-, the First Dialkyl Derivative of a Carbonylmetalate Trianion, and Related Anionic Species
Warnock, Garry F. P.,Moodie, Cammarano Lyn,Ellis, John E.
, p. 2131 - 2141 (2007/10/02)
Treatment of hexamethylphosphoroamide (HMPA) solutions of trisodium tetracarbonylmetalates(3-) of manganese and rhenium with excess liquid ammonia causes precipitation of very thermally stable materials (dec >300 deg C) that are isolated in high yields (85-95percent) and represent the first available pure samples of unsolvated Na3.Infrared and 1H NMR spectral studies of the protonation of Na3 in HPMA show initial formation of the new monohydrides, HM(CO)42-, which are then converted quantitatively to the dihydrides H2M(CO)4-.The new manganese dihydride, which is isoelectronic with the first known carbonyl hydride, H2Fe(CO)4, and the previously established rhenium complex are isolated in high yields (75-80percent) as the pure salts, , The monohydride dianions, HM(CO)42-, also react with Ph3SnCl to provide cis-H(Ph3Sn)M(CO)4-, which can be isolated as the Et4N+ salt for rhenium.The initial successful alkylation reactions of carbonylmetalates(3-) are also reported.Treatment of Na3 with methyl p-toluenesulfonate (MeOTs) in HPMA first provides MeRe(CO)42- (identified by IR), which can be protonated or further methylated to give cis-H(Me)Re(CO)4- or cis-(Me)2Re(CO)4-, both of which are isolated in good yields (70-80percent) as Ph4E+ (E=P, As) salts.These represent the first isolated alkyl derivatives of metal carbonyl trianions.IR, 1H, 13C NMR spectra also confirm that Na3 reacts with 1,4-butaneditosylate to provide solutions of the somewhat thermally unstable rhenacyclopentane CH2CH2CH2CH2Re(CO)4-, the initial example of an anionic 18-electron metallacycloalkane.Infrared, 1H, and 13C NMR spectral data have been obtained for many of these compounds and are compared with those of analogous previously known iron and osmium species.
