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Let \\(\\Delta_{\\mathfrak{X}}\\) be the corresponding sub-Laplacian, and let  \\[ |\\!|\\mathfrak{X}^2f|\\!|_{L^2(G)}^2:=\\int_G \\sum\\limits_{(X,Y)\\in\\mathfrak{X}\\times\\mathfrak{X}}|XYf|^2\\text{d}\\mu  \\]  be the norm of the matrix of second order horizontal derivatives. In this paper, the authors are concerned with the best constant \\(C\\) in the subelliptic Friedrichs-Knapp-Stein inequality  \\[ |\\!|\\mathfrak{X}^2f|\\!|_{L^2(G)}^2\\leq C|\\!|\\Delta_{\\mathfrak{X}}f|\\!|_{L^2(G)}. \\]  By looking at the case of \\(SO(n),\\) \\(n\\geq 4\\), one sees that a semisimple compact Lie group can be endowed with a variety of subelliptic structures, whence the estimates on the constant \\(C\\) above may vary with the structure. The authors consider here a subelliptic structure that naturally appears as the result of the root-space decomposition associated with the Cartan subalgebra. 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