[Mo{N₂C(S)SC₂H₅}{NH₂NC(S)SC₂H₅}{(CH₃)₂NCS₂}₂]‐A Sulfur‐Rich Haptacoordinated Diazenidohydrazido(1–) molybdenum Complex

Abstract

In competition experiments with heptanal/diethyl ketone (1 : 1) it could be shown that 1, 3b and 4b olefinate aldehyde groups without the keto groups being attacked.Presumably the carbonyl olefinations proceed as formulated for lc7l. The postulated product 2a, however, has so far evaded detection. 933.[21 Procedure for synthesis of 1 : A suspension of Mo02(Me2NCS2)2 (3.25 mmol) and NHZNHC(S)SEt (16 mmol) in 60 mL methanol is stirred for 4 Angew. Chem. Int. Ed. Engl. 22 (1983) No. 3 0 Verlag Chemie GmbH. 6940 Weinheim, 1983 0570-0833/83/0303-0245 $02.50/0

Reactions of oxomolybdenum(VI) hydroxamate and thiohydroxamate complexes with hydrazines. Syntheses and structures of a diazenido-hydrazido(1-) complex containing an "end-on"-bonded hydrazido(1-) ligand and of a diazene-diazenido(1-) derivative

“…From the stereochemical point of view there seems to be a tendency for the present molecules to achieve six-coordination rather than seven as sometimes found in related dithiocarbamate species. 13,32 This may relate to the "bite" size of these chelating groups and perhaps gives an added stabilizing influence in the present five-membered-ring chelates which would explain some of the differences. Interestingly, complexes of stoichiometry and structure similar to those of II have been reported, of formula [Mo(NHNC(S)Ph)(N2C-(S)Ph) (PhC(S)NN=CMe2) ], but prepared by a different route,19 Two waters of crystallization (oxygen 0(5)) were found per unit cell and were included in the refinement.…”

“…13,30 This same rearrangement occurs with a tetradentate S2N2 coligand.7 Under similar conditions, however, the mixed hydrazido( 1 -)-diazenido complex [Mo(NH2NC(S)SR)(N2C(S)SR)(dmtc)2], being similar in stoichiometry to I but containing seven-coordinate Mo and a chelating M-NH2NR moiety, could be obtained, which, like I, did not convert to the corresponding bis(diazenido) derivative. 32 Clearly, there are many subtle effects involved that are difficult to quantify.…”

Copper(II) and copper(I) complexes with a bidentate hydrazinic dithiocarbazate: synthesis and crystal structures

“…Hard nitrogen and soft sulfur donor atoms are co-present in the structure of important multidentate ligands such as dithiocarbazates, thiosemicarbazones and bis-thiosemicarbazones. Given the presence of the N,S donor set, these ligands coordinate a wide range of transition and non-transition metal ions [21][22][23] , generating stable complexes with promising pharmacological properties including antifungal, antibacterial, and antitumor activities 7,[24][25][26][27][28][29][30][31][32][33] . Among these, copper(II) compounds appear to be promising candidates due to their cytotoxic activity against human cancer cell lines 2,6,7,28,31,[34][35][36][37][38] .…”

“…It should be noted that most of the coordination structures reported so far include complexes of the dithiocarbazic acid and its S-alkyl/aryl esters in the form of Schiff bases with divalent metal cations 25,26,28,29,33 . Meanwhile, only a few examples of transition metals coordinated by the hydrazine nitrogen of dithiocarbazate are present in the literature 27,30,32,50,51,[63][64][65][66][67] . To the best of our knowledge, little effort has been made so far in the research of copper complexes with dithiocarbazate ligands in which the metal is coordinated by the hydrazinic nitrogen and in the absence of thione-thiol tautomerism.…”