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Smith, a full board director at Legal & General, will leave L&G to take up her new position in January 2005, replacing outgoing chief executive John Handby, former IT director of Glaxo, Powergen and Royal Mail.
The National Computing Centre acquired CIO-Connect last year.
Smith said, "The current membership offering delivers the environment for sharing experiences, networking and influencing suppliers to provide real solutions to chief information officers' real problems.
"I expect also to take advantage of the wealth of offerings in the other parts of the NCC that will help chief information officers take control of their organisations' IT directions and agendas rather than be reliant on external consultancy advice," she said.