Hydrosulfido complexes

Related to the zinc hydroxide complexes [TpRR]ZnOH, the hydrosul-fido complex [TpBut]ZnSH has been synthesized by the reaction of [TpBut]ZnH with H2S (80). However, the corresponding hydrosulfido complex [TpPh]ZnSH was not isolated from the reaction of the less sterically demanding derivative [TpPh]ZnBul with H2S, which gave preferentially the sandwich complex [TpPh]2Zn because of ligand redistribution (81b). 

Hydrosulfido complexes, 517 bonding, 519 reactivity, 519 structures, 519 synthesis, 518 types, 518 Hydroxamates metal complexes, 505-508 Hydroxamic acid, N-methyl-metal complexes, 507 Hydroxamic acid, phenyl-metal complexes stability, 506 Hydroxamic acids... 

The reaction of [tris(3-p-tolylpyrazolyl)hydroborate)]MgMe with H2S produces the monomeric hydrosulfido complex [tris(3-p-tolylpyrazolyl)hydroborate)]MgSH, which has been structurally authenticated the Mg—S bond length is 2.35 A.Other monodentate sulfur ligands include 2-(l-methylethyl)-l,3-dimethyl-l,3,2-diazaphosphorinane 2-sulfide, whose lithium complex has been modeled with molecular orbital calculations, l,3-dimethyl-2-benzylide- 2-thioxo-1,3,2-diazaphosphorinane-S,S), and A-diisopropoxythiophosporylthiobenzamine. ... 

Reaction of the bis(hydrosulfido) complex Cp Rh(SH)2(PMe3) with CpTiCl3 in the presence of NEt3 leads to the formation of the sulfido-bridged titanium-rhodium complex CpClTi(//2-S)2RhCp (PMe3), the molecular structure of which has been determined by X-ray diffraction studies.1784... 

In some cases the oxidative addition reaction has been observed to proceed further with the elimination of dihydrogen and the consequent formation of a stable sulfido complex, in a way the reverse reaction of the activation of hydrogen by Cp 2Ti=S described in the preceding section. For instance, the Zr(n) complex Cp 2Zr(CO)2 reacts with excess HjS in the presence of pyridine to yield the corresponding bis(hydrosulfido) derivative Cp Zr(SH),. This reaction takes place via an initial oxidative addition of HjS to yield Cp Zr(H)(SH) followed by hydrogen elimination in the presence of pyridine to form a terminal sulfido complex Cp Zr(S)(py) the latter undergoes a second oxidative addition of H2S to finally produce the bis(hydrosulfido) complex, as shown in Eq. 5.14 [2]. 

The pAT values of hydrosulfido complexes have never been investigated in detail, although a huge number of hydrosulfido complexes are known [40]. During our continuous study on the reactivities of coordinated dinitrogen, we have... 

Hydrosulfido complexes, which contain M-SH groups, can react by an additional pathway unavailable to metal-thiolate complexes. Hydrosulfido complexes can react by cleavage of the S-H group to generate metal-sulfido complexes. The synthesis and reactivity of sulfido complexes are described in Qrapter 13 (metal-ligand multiple bonds). 

Gerbino DC, Hevia E, Morales D, et al. A new reactivity pattern of low-valent transition-metal hydroxo complexes straightforward synthesis of hydrosulfido complexes via reaction with carbon disulfide. Chem Commun. 2003 328—329. 

The diruthenium /i-hydrosulfido complex 88 reacted with a monometallic hydride complex to yield bis(/it3-sulfido) complex 89 having a terminally bonded chloro ligand (Equation (33)). The hydrido derivative 90 was obtained by the treatment of 89 with NaBH4. 

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