Methyl transfer in the reaction of IrMe3(PMe2Ph)3 with Cu(NCMe)4+

Alvarez, Dan; Caulton, Kenneth G.

doi:10.1016/s0277-5387(00)81225-5

Cited by 5 publications

(4 citation statements)

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“…A series of cluster compounds [3][4][5][6][7][8][9][10][11][12][13][14] of the general type [Fe4S4(LS3)-L']z", where z = 1, 2, or 3 and V is a mono-, bi-, or tridentate ligand, were prepared by chloride substitution of cluster 1 in the reactions illustrated in Figure 2. Clusters 3, 7b, 11, and 14 were generated in solution but not isolated.…”

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confidence: 99%

“…NMR (anion): 2.24 (4'-Me), 3.56 (4-Me), 3.92 (6-Me), 4.65 (2-H), 6.64 (3'-H), 7.19 (2'-H), 7.51 (TV-Me), 8.25 (5-H). Absorption spectrum: Xmax (<M) 300 (sh, 54000), 440 (sh, 12000) nm.…”

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confidence: 99%

“…2.24 (4'-Me), 3.87 (4-Me), 4.29 (6-Me), 6.55 (3'-H), 7.13 (2'-H), 8.53 (5-H), 8.67 (CH2), 12.89 (CH2). Absorption spectrum: Xmax (tM) 303 (sh, 57 000), 488 (10400) nm.…”

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confidence: 99%

“…The mixture was maintained at -20 °C for 2 h. The dark brown microcrystalline solid was collected by filtration, washed with ether, and dried to yield 185 mg (51%) of product. NMR (anion): 2.24 (4'-Me), 3.66 (4-Me), 4.10 (6-Me), 5.43 (hbt-H"), 5.83 (hbt-Hd), 6.65 (3'-H), 7.11 (2'-H), 8.37 (5-H), 9.52 (hbt-Hc), 10.32 (hbt-Ha). Absorption spectrum: Xmx (eM) 300 (60000), 420 (sh, 13000) nm.…”

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Subsite-differentiated analogs of native iron sulfide [4Fe-4S]2+ clusters: preparation of clusters with five- and six-coordinate subsites and modulation of redox potentials and charge distributions

Ciurli¹,

Carrié²,

Weigel³

et al. 1990

J. Am. Chem. Soc.

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product indicate the composition [M(dien)z]2+[HOC(CF3)20-]2,in which the metal is complexed by two triamine ligands to give a large, stable dication with octahedral coordination. The structure of the fluorinated anion is unclear; it is different from that reported previously by Roesky et al. where the complex dianion [H2(OC-(CF3)20H}2-] containsfour diol residues." Since the latter had been made by the hydrolysis of the anion [(CF,),C=NC(C-F,),O-], we repeated the synthesis by the direct reaction of aqueous (CF,),C(OH), with base in the presence of large cations (Et,N+, Ph4P+, Ph4Ast); in each case, the product isolated contained the same [ H2(OC(CF3)20H)42-] dianion. It seems likely that the structure of the loosely bonded free anion formed from the diol is easily influenced by the nature of the counterion present, and investigation of this point is continuing. ConclusionsThese results clearly establish the preferred modes of coordination of hexafluoropropane-2,2-diol. In the diionized form, it chelates to a variety of metal ions, with bridging found only with ions such as Au+, where the formation of small rings is disfavored. The reduction of basicity of the alkoxides accompanying fluorination causes them to coordinate to one metal center only; it is not surprising this ligand does not form a polyoxomolybdate cluster complex analogous to that derived from CH2(0H)2.2 The formation of complexes containing six-membered rings results from the increased stability of the ethereal linkage found in fluorinated systems and the ease with which it is formed by a template condensation reaction.We conclude that the ready availability and unique properties of (CF3)2C(OH)2 make it particularly suitable for reaction with a large variety of metal ions to produce stable complexes.

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confidence: 99%

“…NMR (anion): 2.24 (4'-Me), 3.56 (4-Me), 3.92 (6-Me), 4.65 (2-H), 6.64 (3'-H), 7.19 (2'-H), 7.51 (TV-Me), 8.25 (5-H). Absorption spectrum: Xmax (<M) 300 (sh, 54000), 440 (sh, 12000) nm.…”

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confidence: 99%

“…2.24 (4'-Me), 3.87 (4-Me), 4.29 (6-Me), 6.55 (3'-H), 7.13 (2'-H), 8.53 (5-H), 8.67 (CH2), 12.89 (CH2). Absorption spectrum: Xmax (tM) 303 (sh, 57 000), 488 (10400) nm.…”

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