The limiting value of ZDMC formation: new insight into the reaction of ZNO and TMTD

✍ Scribed by P. J. Nieuwenhuizen; M. Van Duin; J. G. Haasnoot; J. Reedijk; W. J. Mcgill

• Book ID: 101256253
• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 181 KB
• Volume: 73
• Category: Article
• ISSN: 0021-8995
• DOI: 10.1002/(sici)1097-4628(19990815)73:7<1247::aid-app19>3.0.co;2-f

✦ Synopsis

The reaction of ZnO and tetramethylthiuram disulfide (TMTD) was reinvestigated in detail. Under conditions where evaporation of volatiles is possible, TMTD and an excess of ZnO are found to produce bis(dimethyldithiocarbamato)zinc(II) (ZDMC) in limiting amounts close to 60 mol %, irrespective of the ratio between ZnO and TMTD. This result points to the operation of more than one route toward ZDMC. When ZnO and TMTD are reacted in closed vessels in inert atmosphere, a nucleophilic reaction of ZnO with TMTD was confirmed by GC-mass spectroscopy (MS) detection of COS and NMR observation of tetramethylthiourea (TMTU). This route is found to account for about 70 mol % of the total amount of ZDMC formed. A previously unrecognized redox reaction between ZnO, sulfur, and TMTD, furnishing ZnSO 4 and ZDMC, is responsible for approximately 15 mol % of the amount of ZDMC. Other products that were detected are CO 2 , CS 2 , and tetramethylurea, whereas ZnSO 3 , ZnS, and dioxygen were absent. Based on the latter observation, the operation of a mechanism constituting radical reduction of water by TMTD, yielding dioxygen, was excluded.