Voinovich, a Republican continues to speak out against John Bolton's nomination before the vote on the Senate floor.
Bolton was passed to the Senate floor without the customary committee approval.
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The Republican senator who snubbed the White House by opposing John Bolton's nomination for US ambassador to the United Nations on Tuesday took the unusual move of asking his colleagues to vote against Mr Bolton.
George Voinovich, an Ohio Republican, wrote a letter to his fellow senators, arguing that the appointment of Mr Bolton, the outgoing undersecretary of state for arms control, would hurt US efforts to improve relations with its allies.
"John Bolton's nomination sends a negative message to the world community," Mr Voinovich wrote.
"In these dangerous times, we cannot afford to put at risk our nation's ability to successfully wage and win the war on terror with a controversial and ineffective Ambassador to the United Nations."
The Senate foreign relations committee two weeks ago sent Mr Bolton's name to the full Senate for approval. But in a highly unusual move triggered by Mr Voinovich's opposition to the nomination, Richard Lugar, the Republican committee chairman, agreed to send the nomination to the Senate without a recommendation.
In a move that is likely to upset the White House, Mr Voinovich on Tuesday argued that the appointment of Mr Bolton would impede US efforts to rebuild relationships with key allies that were damaged over the controversy surrounding the Iraq war.
"At a time when the United States strives to fight terrorism globally, to build a stable and free Iraq, to find a peaceful resolution to the nuclear ambitions of Iran and North Korea, to spread democracy in the place of oppressive regimes, and to enact needed reforms at the United Nations, it is imperative that we have the support of our friends and allies internationally," he wrote.
The move comes as Bill Frist, the Republican senate majority leader considers pushing for a vote on Mr Bolton this week. It also comes on the heels of a bipartisan deal in the Senate, which would prevent Democrats from filibustering - a parliamentary move that requires 60 votes in the 100 seat Senate to overcome - judicial nominations.
One Senate aide on Tuesday said the Democrats have not decided whether they would attempt to filibuster Mr Bolton. The Senate foreign relations committee spent several weeks investigating allegations that Mr Bolton skewed intelligence and attempted to sideline intelligence analysts who refused to endorse his conclusions. After the investigation, most Republicans rejected the charges, saying the Democrats were playing politics.
Democrats are also frustrated that they have not been briefed on National Security Agency intelligence intercepts that Mr Bolton requested, and that they have not been given access to the State Department documents they requested for their investigation.