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Medientyp:
E-Artikel
Titel:
Nucleophilic Addition of Water and Alcohols to Dicyanonitrosomethanide: Ligands with Diverse Bonding Modes in Magnetically Coupled d‐Block Complexes
Beteiligte:
Chesman, Anthony S. R.;
Turner, David R.;
Moubaraki, Boujemaa;
Murray, Keith S.;
Deacon, Glen B.;
Batten, Stuart R.
Erschienen:
Wiley, 2010
Erschienen in:European Journal of Inorganic Chemistry
Beschreibung:
<jats:title>Abstract</jats:title><jats:p>Ligands resulting from the transition‐metal‐promoted nucleophilic addition of water or an alcohol to dicyanonitrosomethanide ions (dcnm) have been utilised in the formation of a large series of polynuclear complexes. Addition of water to dcnm results in formation of carbamoylcyanonitrosomethanide (ccnm); deprotonation of this ligand gives amidocarbonyl(cyano)nitrosomethanide (acnm), which has been incorporated into the trinuclear complex [Cu<jats:sub>3</jats:sub>(acnm)<jats:sub>2</jats:sub>(dmae)<jats:sub>2</jats:sub>(H<jats:sub>2</jats:sub>O)<jats:sub>2</jats:sub>] [dmae = 2‐(dimethylamino)ethoxide] (<jats:bold>1</jats:bold>) which shows strong antiferromagnetic coupling with an exchange coupling constant, <jats:italic>J</jats:italic> = –500 cm<jats:sup>–1</jats:sup>. [Cu(acnm)(NH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>]<jats:sub>∞</jats:sub> (<jats:bold>2</jats:bold>) marks the first instance of acnm facilitating the formation of a coordination polymer, namely a 1D chain with intramolecular hydrogen bonding. Attempts to synthesise <jats:bold>2</jats:bold> through different reaction conditions instead resulted in the mononuclear [Cu(acnm)(NH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>(py)] (py = pyridine) (<jats:bold>3</jats:bold>). The addition of ethanol to dcnm results in cyano[imino(ethoxy)methyl]nitrosomethanide (cenm) which features in the mononuclear [Cu(cenm)<jats:sub>2</jats:sub>(H<jats:sub>2</jats:sub>O)<jats:sub>2</jats:sub>] (<jats:bold>4</jats:bold>) and polymeric {[Cu(cenm)<jats:sub>2</jats:sub>]<jats:sub>2</jats:sub><jats:bold>·</jats:bold>H<jats:sub>2</jats:sub>O}<jats:sub>∞</jats:sub> (<jats:bold>5</jats:bold>). The latter is the first example of the cenm ligand in a coordination polymer and has a highly unusual coordination mode through the nitrile groups and extremely weak antiferromagnetic coupling. {[Mn<jats:sub>3</jats:sub>(ccnm)<jats:sub>2</jats:sub>(EtOH)<jats:sub>2</jats:sub>(OAc)<jats:sub>4</jats:sub>]<jats:bold>·</jats:bold>2EtOH}<jats:sub>∞</jats:sub> (<jats:bold>6</jats:bold>) and (Et<jats:sub>4</jats:sub>N)<jats:sub>2</jats:sub>[Cu(ccnm)<jats:sub>4</jats:sub>] (<jats:bold>7</jats:bold>) contain previously unobserved coordination modes of the ccnm ligand while the complex [Mn(cmnm)<jats:sub>3</jats:sub>Mn(bipy)(MeOH)](ClO<jats:sub>4</jats:sub>) (<jats:bold>8</jats:bold>) {cmnm = cyano[imino(methoxy)methyl]nitrosomethanide, bipy = 2,2′‐bipyridine} displays weak antiferromagnetic coupling between manganese atoms with <jats:italic>J</jats:italic> = –1.44 cm<jats:sup>–1</jats:sup>. A change in the solvent systems used in the synthesis of <jats:bold>7</jats:bold> results in the formation of the mononuclear complexes [Mn(bipy)<jats:sub>2</jats:sub>(dcnm)<jats:sub>2</jats:sub>] (<jats:bold>9</jats:bold>) or [Mn(bipy)<jats:sub>2</jats:sub>(H<jats:sub>2</jats:sub>O)(dcnm)](dcnm)<jats:bold>·</jats:bold>H<jats:sub>2</jats:sub>O (<jats:bold>10</jats:bold>) and [Mn(bipy)<jats:sub>2</jats:sub>(dcnm)(H<jats:sub>2</jats:sub>O)](dcnm) (<jats:bold>11</jats:bold>). The addition of ethlyene glycol monomethyl ether to dcnm gives cyano[imino(2‐methoxyethoxy)methyl]nitrosomethanide (cgnm) and the formation of [Cu(cgnm)<jats:sub>2</jats:sub>(H<jats:sub>2</jats:sub>O)<jats:sub>2</jats:sub>] (<jats:bold>12</jats:bold>).</jats:p>