The way to do this using xp_cmdhsell is as follows:

EXEC master.dbo.xp_cmdshell 'sqlcmd -S ServerNameComesHere -E -d ToolDB -Q "EXEC dbo.InsertTempValue 101" ';

Could you let us know why you are using xp_cmdshell to execute a stored procedure - depending on what you want to achieve there might be other options available.