Die Titelverbindungen wurden durch Reaktion des Liganden mit Co‐ bzw. Ni‐nitrat dargestellt und durch IR‐Spektren charakterisiert.

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A simple method for calculating the oxidation state of Cr in complexes containing only Cr-O bonds is presented. A total of 242 CrOn fragments with n = 3-6 were retrieved from the Cambridge Structural Database (CSD) and, together with the data for K3CrO8, were analyzed using the bond valence sum method. New R0 values for Cr(II) of 1.739(21) A, Cr(III) of 1.708(7) A, Cr(V) of 1.762(14) A, and Cr(VI) of 1.793(7) A were derived. An average R0 value of 1.724 A for Cr-O reproduces the oxidation state of 96 of the 110 Cr(II), Cr(III), and Cr(IV) CrOn complexes (n = 3-6) and that of K3CrO8 within 0.30 valence units. The crystal structure of K3CrO8 was redetermined at 173 K to provide accurate data for a Cr complex with both high oxidation state and coordination number. Potassium tetraperoxochromate(V), K3CrO8, is tetragonal, Space group I42m, a = b = 6.6940(3) A, c = 7.7536(5) A, Z = 2. The difficulties with fitting the observed valence for Cr(V) and Cr(VI) complexes with coordination numbers 4 and 5 are discussed. The use of bond valence sums in gaining chemical insight into Cr complexes with noninnocent ligands and in establishing oxidation states in Cr clusters is presented. An analysis of the Cr-O bond distances used in the calculations shows a large range of values that can be understood in terms of the bond valence sum calculation.

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Inorg. Chem. 1985, 24, 4435-4437 4435 and cresoxide but not bound triphenyl phosphite. When I and P(OC6H4CH3)3 were combined in CDC13, 31P N M R and G C analysis showed that phosphite exchange was facile at room temperature.The complete phenol deuteration reaction catalyzed by I is shown in Scheme I.Steps a and b were shown previously' and are confirmed by the present work. Complete ortho deuteration of the triphenyl phosphite ligands of I1 was shown by mass spectroscopy and I3C NMR. Facile exchange of triphenyl phosphite (the equilibrium of step c), was shown by 31P NMR. Intermediate I11 is probably a five-coordinate Ru(I1) complex for which there is ample precedence.6 The transesterification reaction on free triphenyl phosphite was demonstrated by 31P N M R and GCMS.These results confirm that D, selectively deuterates the ortho positions on the triphenyl phosphite ligands of I. Catalytic deuteration of phenol was greatly accelerated only by the addition of a transesterification cocatalyst. This study represents the first example of catalysis via an ortho metalated ~o m p l e x .~~~~* Extension of this work to other insertable groups (other than D2) is under study.Acknowledgment. Hans Grade and Steve Dorn are acknowledged for their skilled mass spectroscopic analysis. Cindy Herderich is thanked for her help in preparation of the manuscript. George Parshall, Du Pont, is thanked for reading a preprint of the manuscript and for providing some helpful suggestions.