3 research outputs found
Redox Properties of Heterometallic Osmium Cluster Compounds
ΠΠ»Π΅ΠΊΡΡΠΎΡ
ΠΈΠΌΠΈΡΠ΅ΡΠΊΠΈΠΌΠΈ ΠΌΠ΅ΡΠΎΠ΄Π°ΠΌΠΈ ΠΈΠ·ΡΡΠ΅Π½Ρ ΡΠ΅Π΄ΠΎΠΊΡ-ΡΠ²ΠΎΠΉΡΡΠ²Π° Π³Π΅ΡΠ΅ΡΠΎΠΌΠ΅ΡΠ°Π»Π»ΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠ΅ΡΡΡΠ΅Ρ
ΡΡΠ΄Π΅ΡΠ½ΡΡ
Π°Π½ΠΈΠΎΠ½Π½ΡΡ
[Os3Fe(ΞΌ-H)(CO)13]β, [Os3Co(CO)13]β ΠΈ Π½Π΅ΠΉΡΡΠ°Π»ΡΠ½ΡΡ
Cp*MOs3(CO)10(ΞΌ-H)
(ΞΌ-Cl) (M = Rh, Ir) ΠΊΠ»Π°ΡΡΠ΅ΡΠΎΠ² Π² Π°ΡΠ΅ΡΠΎΠ½ΠΈΡΡΠΈΠ»Π΅ ΠΈ Π΄ΠΈΡ
Π»ΠΎΡΠΌΠ΅ΡΠ°Π½Π΅ Π½Π° ΠΏΠ»Π°ΡΠΈΠ½ΠΎΠ²ΠΎΠΌ, ΡΡΠ΅ΠΊΠ»ΠΎΡΠ³Π»Π΅ΡΠΎΠ΄Π½ΠΎΠΌ
ΠΈ ΡΡΡΡΠ½ΠΎΠΌ ΠΊΠ°ΠΏΠ΅Π»ΡΠ½ΠΎΠΌ ΡΠ»Π΅ΠΊΡΡΠΎΠ΄Π°Ρ
. ΠΠΎΠΊΠ°Π·Π°Π½ΠΎ, ΡΡΠΎ Π² ΡΠ΅Π·ΡΠ»ΡΡΠ°ΡΠ΅ ΡΠ΅Π΄ΠΎΠΊΡ-ΠΏΡΠ΅Π²ΡΠ°ΡΠ΅Π½ΠΈΠΉ Π²ΡΠ΅Ρ
ΠΈΠ·ΡΡΠ΅Π½Π½ΡΡ
Π³Π΅ΡΠ΅ΡΠΎΠΌΠ΅ΡΠ°Π»Π»ΠΈΡΠ΅ΡΠΊΠΈΡ
ΠΊΠ»Π°ΡΡΠ΅ΡΠΎΠ² ΠΏΡΠΎΠΈΡΡ
ΠΎΠ΄ΠΈΡ ΡΠ»ΠΈΠΌΠΈΠ½ΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ M-ΡΠΎΠ΄Π΅ΡΠΆΠ°ΡΠΈΡ
(Π = Fe, Co, Rh, Ir) ΡΡΠ°Π³ΠΌΠ΅Π½ΡΠΎΠ² ΠΈ ΠΎΠ±ΡΠ°Π·ΠΎΠ²Π°Π½ΠΈΠ΅ Π³ΠΎΠΌΠΎΠΌΠ΅ΡΠ°Π»Π»ΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΡΠ΅Ρ
ΡΡΠ΄Π΅ΡΠ½ΡΡ
ΠΊΠ»Π°ΡΡΠ΅ΡΠΎΠ²
ΠΎΡΠΌΠΈΡ, ΡΡΠ°ΡΡΠ²ΡΡΡΠΈΡ
Π² Π΄Π°Π»ΡΠ½Π΅ΠΉΡΠΈΡ
ΡΠ»Π΅ΠΊΡΡΠΎΡ
ΠΈΠΌΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠ΅Π°ΠΊΡΠΈΡΡ
The redox properties of heterometallic anionic [Os3Fe(ΞΌ-H)(CO)13]β, [Os3Co(CO)13]β and neutral
Cp*MOs3(CO)10(ΞΌ-H)(ΞΌ-Cl) (M = Rh, Ir) clusters were studied by electrochemical methods at platinum,
glassed carbon and dropping mercury electrodes in acetonitrile and dichloromethane solutions. It was
established that redox transformations of these heterometallic clusters results in the elimination of
M-containing (Π = Fe, Co, Rh, Ir) fragments and the formation of homometallic trinuclear osmium
clusters, which undergoes further electrochemical reaction
Unusual Synthesis of Triosmium Carbene Clusters by Tandem Activation of Chlorohydrocarbons and Heterocyclic Amines
Reactions of the [Os3H2(CO)(10)] cluster complex (1) with six-membered heterocyclic amines (morpholine, thiomorpholine, piperidine) and halohydrocarbons (CH2Cl2, ClHC=CHCl, CH2=CCl2) at similar to 25 degrees C have been studied. Two main types of products are formed in all studied reactions. One product is carbene cluster [Os-3(mu-H)(mu-Cl){eta(1)-C(CH3)N(CH2CH2)(2)X}(CO)(9)] (X=O, S, CH2) (3, 3 a and 3 b). Second product is cluster containing enamine ligand [Os-3(mu-H){mu-CH=CHN(C2CH2)(2)X)}(2)(CO)(10)] (X=O, S, CH2) (2, 2 a and 2 b). The carbene ligand is assembled on a cluster, from three organic molecules, thus representing the first example of carbene ligands formed in this way. Clusters with carbene ligand exist as two stable isomers (rotamers hindered towards the Os-C bond), as confirmed by NMR studies and conformational analysis. We have found that in reactions of cluster 1 with acyclic amines containing an oxygen atom in gamma-position (likely morpholine in CH2Cl2), only complexes with bridging enamine ligands are formed. Compounds 2 a, 2 b, 3 and 3 b are characterized by single-crystal X-ray diffraction
Redox Properties of Heterometallic Osmium Cluster Compounds
ΠΠ»Π΅ΠΊΡΡΠΎΡ
ΠΈΠΌΠΈΡΠ΅ΡΠΊΠΈΠΌΠΈ ΠΌΠ΅ΡΠΎΠ΄Π°ΠΌΠΈ ΠΈΠ·ΡΡΠ΅Π½Ρ ΡΠ΅Π΄ΠΎΠΊΡ-ΡΠ²ΠΎΠΉΡΡΠ²Π° Π³Π΅ΡΠ΅ΡΠΎΠΌΠ΅ΡΠ°Π»Π»ΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠ΅ΡΡΡΠ΅Ρ
ΡΡΠ΄Π΅ΡΠ½ΡΡ
Π°Π½ΠΈΠΎΠ½Π½ΡΡ
[Os3Fe(ΞΌ-H)(CO)13]β, [Os3Co(CO)13]β ΠΈ Π½Π΅ΠΉΡΡΠ°Π»ΡΠ½ΡΡ
Cp*MOs3(CO)10(ΞΌ-H)
(ΞΌ-Cl) (M = Rh, Ir) ΠΊΠ»Π°ΡΡΠ΅ΡΠΎΠ² Π² Π°ΡΠ΅ΡΠΎΠ½ΠΈΡΡΠΈΠ»Π΅ ΠΈ Π΄ΠΈΡ
Π»ΠΎΡΠΌΠ΅ΡΠ°Π½Π΅ Π½Π° ΠΏΠ»Π°ΡΠΈΠ½ΠΎΠ²ΠΎΠΌ, ΡΡΠ΅ΠΊΠ»ΠΎΡΠ³Π»Π΅ΡΠΎΠ΄Π½ΠΎΠΌ
ΠΈ ΡΡΡΡΠ½ΠΎΠΌ ΠΊΠ°ΠΏΠ΅Π»ΡΠ½ΠΎΠΌ ΡΠ»Π΅ΠΊΡΡΠΎΠ΄Π°Ρ
. ΠΠΎΠΊΠ°Π·Π°Π½ΠΎ, ΡΡΠΎ Π² ΡΠ΅Π·ΡΠ»ΡΡΠ°ΡΠ΅ ΡΠ΅Π΄ΠΎΠΊΡ-ΠΏΡΠ΅Π²ΡΠ°ΡΠ΅Π½ΠΈΠΉ Π²ΡΠ΅Ρ
ΠΈΠ·ΡΡΠ΅Π½Π½ΡΡ
Π³Π΅ΡΠ΅ΡΠΎΠΌΠ΅ΡΠ°Π»Π»ΠΈΡΠ΅ΡΠΊΠΈΡ
ΠΊΠ»Π°ΡΡΠ΅ΡΠΎΠ² ΠΏΡΠΎΠΈΡΡ
ΠΎΠ΄ΠΈΡ ΡΠ»ΠΈΠΌΠΈΠ½ΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ M-ΡΠΎΠ΄Π΅ΡΠΆΠ°ΡΠΈΡ
(Π = Fe, Co, Rh, Ir) ΡΡΠ°Π³ΠΌΠ΅Π½ΡΠΎΠ² ΠΈ ΠΎΠ±ΡΠ°Π·ΠΎΠ²Π°Π½ΠΈΠ΅ Π³ΠΎΠΌΠΎΠΌΠ΅ΡΠ°Π»Π»ΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΡΠ΅Ρ
ΡΡΠ΄Π΅ΡΠ½ΡΡ
ΠΊΠ»Π°ΡΡΠ΅ΡΠΎΠ²
ΠΎΡΠΌΠΈΡ, ΡΡΠ°ΡΡΠ²ΡΡΡΠΈΡ
Π² Π΄Π°Π»ΡΠ½Π΅ΠΉΡΠΈΡ
ΡΠ»Π΅ΠΊΡΡΠΎΡ
ΠΈΠΌΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠ΅Π°ΠΊΡΠΈΡΡ
The redox properties of heterometallic anionic [Os3Fe(ΞΌ-H)(CO)13]β, [Os3Co(CO)13]β and neutral
Cp*MOs3(CO)10(ΞΌ-H)(ΞΌ-Cl) (M = Rh, Ir) clusters were studied by electrochemical methods at platinum,
glassed carbon and dropping mercury electrodes in acetonitrile and dichloromethane solutions. It was
established that redox transformations of these heterometallic clusters results in the elimination of
M-containing (Π = Fe, Co, Rh, Ir) fragments and the formation of homometallic trinuclear osmium
clusters, which undergoes further electrochemical reaction