Oct. 20, 1961
4167
HETERO-BINUCLEAR CHELaTES O F COPPER(II)AND SILVER(1) TABLE IV STREXCTHS OF THE ABSORPTION BAI~DS' OSCILLATOR
Compound
Solrent
CH3CN CH3Iion 0 . 1 ill ((c6Hj)~MeP)Clin CHzNOz ((CfiHd4Ph [NiBrd CH3Xo2 CH3CN 0 . 1 111 ( ( C 6 H a ) S - ? ~ - B ~ in P ) CH3CPi Br in'i ((CsH.&P0)2Br?I Acetone [Ni((CsH5)3PO)zI21 CsHjCl C~H~CI [%((C~H&ASO)ZC~~] [Ni((CsH&AsO)&'d C&,CI a The estimates include all absorption in the region of the v i concerned. sorption known to be due to solvolyzed species is included.
heavy ultraviolet absorption trailing off into the region of v3 makes accurate intensity assessment difficult. The most striking aspect of the intensity data is the relatively high intensity of the bands of the tetrahedral nickel(I1) complexes as compared to the band intensities for octahedral complexes of nickel(I1). The ratio is about l o 2 . This effect is quite general, having been found for Co(II),21s22Mn(II)23,24and Cu(II),17 and Ballhausen and Liehr have discussed the possible reasons for it.*& The intensity ratios show that (22) F. A. Cotton and M. Goodgame, J . A m . Chem. SOC.,83, 1777 (1961). (23) D. M . L. Goodgame and F. A. Cotton, J . Chem. SOC., Aug.(l961). (24) F. A. Cotton, D. M. L. Goodgame and M. Goodgame, J . A m . Chem. SOC.,in press. ( 2 5 ) C. J. Ballhausen and A. D. Liehr, J . Mol. Spect., 2, 342 (1958); 4 , 190 (1960).
[COXTRIBUTION FROM
THE
f Y?
fva
((CsHd3MeP)~[NiCl4l
fu3/fV2
2 30 x 10-3 2 . 0 1 x 10-4 2.21 x 10-3 2.35 X 2 . 2 4 x 10-3 1.42 X lo-' 3.12 x 10-3 4.85 x 10-4 2.97 X 4.28 X lo-' 3.15 X 2.61 X 1.59 x 10-3 1.63 x 10-4 2 06 x 10-3 1 08 X 1.52 x 10-3 1 21 x 10-4 1.79 x lo-' 2.92 x 10-3 Thus, for the v2 bands, the intensity
11.4 9.40 15 8 6.44 6.94 12.1 9.75 19.1 12.6 16.3 of the ab-
v3 is generally 10 to 20 times stronger than v2. This is in agreement with the fact that in the strong field limit v3 remains a one-electron transition while v2 becomes a two-electron transition. It is also noteworthy that the intensity of v 3 is relatively insensitive to solvolysis effects, whereas for v2 the solvolyzed species are more strongly absorbing than are the [NiX4I2-ions.
Acknowledgments.-The generous financial support of the United States Atomic Energy Commission (Contract No. AT(30-1)-1965) is gratefully acknowledged. \Ire thank Professor H. G. Drickamer and Dr. Herbert TVeakliem for informing us of some of their results in advance of publication and Dr. A. I). Liehr for sending us some numerical results of the Liehr and Ballhausen calculations.
POLYTECHNIC INSTITUTE OF BROOKLYN, BROOKLYS,~ ' E WYORK,A K D MICHIGAN,ANNARBOR,MICHIGAS]
THE
UXIVERSITY OF
Hetero-binuclear Chelates of Copper(I1) and Silver(1) BY
c. H. LIUA4ND CHUI FANLIU RECEIVED MAY4, 1961
Interaction between silver(1) ion and bis-(pyridine-2-aldoxime)-copper(II)ion has been investigated by potentiometric measurements. The hetero-binuclear chelate involved has also been isolated as the perchlorate and examined by infrared spectroscopy.
In a previous investigation,l it has been shown groups. The present work is concerned with the that monohydrogen bis-(pyridine-2-aldoxime)-cop- interaction between the complex ion and silver(1) per(I1) ion has the structure ion. This interaction has been studied by measuring the two competing equilibria r1HC+
I
