Abstract
The dodecacarbonylhexanickelate(2−) dianion, [Ni 6(CO) 12] 2−, has been studied by infrared spectroscopy in tetrahydrofuran and acetonitrile solutions under applied high pressures of carbon monoxide or syngas (CO/H 2=1:2) both at 25 and 100 °C. The dianion is converted, possibly by fragmentation, to other carbonyl clusters via the dodecacarbonylpentanickelate(2−) dianion, [Ni 5(CO) 12] 2−, under 20 atm. of CO or syngas at 25 °C and primarily to Ni(CO) 4 at a pressure of 20 atm. and at 100 °C. The X-ray crystal structure of [N(PPh 3) 2] 2[Ni 6(CO) 12] is reported and compared with that of the tetramethylammonium analogue, [NMe 4] 2[Ni 6(CO) 12].
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