The comments by Ms Sturgeon’s spokesman follow newspaper reports that the First Minister was made aware of allegations of sexual harassment against her predecessor before a meeting between her and Mr Salmond.
On Sunday, the First Minister referred herself to the watchdog that polices the ministerial code over a series of meetings and telephone conversations between Ms Sturgeon and Mr Salmond.
The Scottish Government lost a legal challenge over its handling of the matter after it emerged that a civil servant in charge of the investigation had prior contact with the two women who lodged the complaints. The case has cost the taxpayer £500,000.
The allegations made by two women, which Mr Salmond denies, remain under investigation by police who have spoken to staff at Bute House.
Speaking to journalists on Monday, the First Minister’s spokesman said: “This appears to be an attempt to smear the First Minister.
“Suggestions by Mr Salmond’s ‘insiders’ that the First Minister knew about the investigation before 2 April are not true.”
“The suggestion put to Ms Sturgeon’s Chief of Staff by the Times, that she knew of complains when she met someone who could be described as an intermediary for Alex Salmond on 6 March, is also not true.”
A spokesman for Mr Salmond was quoted saying in response: “We will not be commenting on the content of private meetings or discussions on or off the record but Alex has made it clear that, if asked, he will be happy to give evidence to the panel of independent advisers [on the ministerial code].
The spokesman added: “In the interests of accuracy it is the case that the First Minister’s senior special adviser knew of the existence of complaints against Alex some time before the meeting of 2 April and that she initiated the first contact through an intermediary.
“They then arranged the meeting [with Ms Sturgeon] which Alex asked for. Alex has no certainty as to the state of knowledge of the First Minister before then.
“In any case we regard this controversy about these meetings as of secondary importance.
Over the weekend, it emerged that a criminal investigation is underway over the leak of details about the allegations to a tabloid newspaper.
The Information Commissioner’s Office confirmed that the Scottish Government is at the centre of an investigation into possible breaches of the Data Protection Act.