Sulfur Nitride Complexes of Nickel

Submitted by D. T. HAWORTH, J. D. BROWN, and Y. CHEN Checked by WILLIAM L. HOLDERt and WILLIAM L. JOLLyT 

The first fraction eluted is green, the second fraction is red, and a third purple-colored fraction remains on the column. The solid remaining in the flask is extracted further with two 100-mL portions of acetone. The acetone portions, when put on the column, slowly elute the purple fraction. The purple fraction is eluted completely by an ethanol/acetone (1 4) solution. 

The deuterated complex can be prepared by dissolving Ni(S2N2H)2 in tetra-hydrofuran and adding a 1000-fold excess of D2O. The mixture is stirred at ambient temperature for 3 hours. The solvent is removed at reduced pressure on a rotary evaporator. The infrared spectrum shows shifts of the 3283 and 3162 cm bands in Ni(S2N2H)2 to 2433 and 2375 cm, respectively, in Ni(S2N2D)2. These are assigned to the N—H and N—D antisymmetric and symmetric stretch-in modes. The 1166 cm band also shows a large shift (182 cm ) on deutera-tion. 

This synthesis can be extended to the preparation of the sulfur nitride complexes of other transition and post-transition metals. Furthermore, Ni(S2N2H)2 can serve as a starting material for the synthesis of many derivatives of this compound by replacement of the acidic N—H proton. Such compounds include substituents on one or two of the nitrogen atoms, as well as groups that bridge the cis-nitrogen atoms. 

(t/5 -CYCL0PENTADIENYL)NITR0SYL complexes OF CHROMIUM, MOLYBDENUM, AND TUNGSTEN 

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