Nicola Sturgeon claimed she was not aware of female civil servants being advised to avoid being alone with former first minister Alex Salmond.
Sturgeon was confronted with the direct question during First Minister's Questions two days after MSPs were prevented from probing the allegation in parliament.
The First Minister said MSPs were "perfectly entitled" to take up this issue and vowed she is "absolutely committed to fully complying with the inquiry".
Her comments came after Holyrood started its probe on the botched Scottish Government investigation into allegations about Salmond when he was in office. He denied all allegations and a judicial review found the investigation was unlawful and bias.
Scotland's top civil servant, Leslie Evans, was first to appear under oath at the Holyrood probe on Tuesday.
Evans said she could not comment on claims that female civil servants were advised not to be alone with the former first minister.
Raising the issue again at First Minister’s Questions today, Tory Murdo Fraser asked if Sturgeon was "herself aware of female civil servants being given that advice?"
She told him: "No, I wasn't."
Sturgeon added that Evans was "happy to write to the committee to address this issue, if the committee wishes".
Scottish Labour deputy leader Jackie Baillie raised wider concerns the government had failed to hand over full documentary details for the probe.
Baillie said: "Given that swathes of documents are heavily redacted and the Scottish Government is refusing access to key documents relating to the core of the inquiry's remit, I hope the First Minister will want to stand by her earlier commitment."
She called on Ms Sturgeon to "instruct the full co-operation that is currently missing from the Scottish Government".
The First Minister said: "I am absolutely committed to fully complying with the inquiry.
"I will personally attend the committee to answer questions when I am asked to do so."
She pledged she would "answer all questions that are put to me when the committee asks me to do, unless of course they asking me questions that my answers would breach legal requirements".
She added that she had already submitted written evidence to the inquiry – saying it was for the committee to decide "when and to what extent" this is made public.
Sturgeon continued: "I have also, given part of the committee remit is to look at my conduct, I have recused myself from any decision-making in terms of the Government's interaction with the committee."
For this reason, she was not going to issue instructions, but added: "The Government will continue to fully co-operate, I am sure, and within the legal obligations that the Government operates under make available the maximum amount of information that it can to the committee."
