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The reactivity of dichloroplatinum(II) complexes containing thioether-functionalized bis(diphenylphosphanyl)amines of formula (Ph<inf>2</inf>P)<inf>2</inf>N(CH<inf>2</inf>)<inf>2</inf>SR (R = (CH<inf>2</inf>)<inf>5</inf>CH<inf>3</inf>, CH<inf>2</inf>Ph) toward group 6 carbonylmetalates Na[M(CO)<inf>3</inf>Cp] (M = Mo or W, Cp = cyclopentadienyl) was explored. Reactions with two or more equivalents of Na[M(CO)<inf>3</inf>Cp] (M = Mo or W) afforded the trinuclear complexes of general formula [PtPh{M(CO)<inf>3</inf>Cp}{?-P(Ph)N(CH<inf>2</inf>CH<inf>2</inf>SR)(PPh<inf>2</inf>)-?<sup>3</sup>P,P,S}M(CO)<inf>2</inf>Cp] (3 M = Mo, R = (CH<inf>2</inf>)<inf>5</inf>CH<inf>3</inf>; 4 M = Mo, R = CH<inf>2</inf>Ph; 9 M = W, R = (CH<inf>2</inf>)<inf>5</inf>CH<inf>3</inf>; 10 M = W, R = CH<inf>2</inf>Ph), the structure of which consists of a six-membered platinacycle condensed with a four-membered M-P-N-P cycle, together with small amounts of isomeric PtM<inf>2</inf> clusters [PtM<inf>2</inf>(CO)<inf>5</inf>Cp<inf>2</inf>{(Ph<inf>2</inf>P)<inf>2</inf>N(CH<inf>2</inf>CH<inf>2</inf>SR)-?<sup>2</sup>P,P}] (5 M = Mo, R = (CH<inf>2</inf>)<inf>5</inf>CH<inf>3</inf>; 6 M = Mo, R = CH<inf>2</inf>Ph; 11 M = W, R = (CH<inf>2</inf>)<inf>5</inf>CH<inf>3</inf>; 12 M = W, R = CH<inf>2</inf>Ph) in which the ligand (Ph<inf>2</inf>P)<inf>2</inf>NR solely chelates the Pt atom or bridges an M-Pt bond as in [PtM<inf>2</inf>(CO)<inf>5</inf>Cp<inf>2</inf>{?-(Ph<inf>2</inf>P)<inf>2</inf>N(CH<inf>2</inf>CH<inf>2</inf>SR)-?<sup>2</sup>P,P}] (7 M = Mo, R = (CH<inf>2</inf>)<inf>5</inf>CH<inf>3</inf>; 8 M = Mo, R = CH<inf>2</inf>Ph; 13 M = W, R = (CH<inf>2</inf>)<inf>5</inf>CH<inf>3</inf>; 14 M = W, R = CH<inf>2</inf>Ph). The synthesis of the trinuclear complexes 3, 4, 9, and 10 entails an unexpected P-phenyl bond cleavage reaction and phenyl migration onto Pt. When only 1 equiv of Na[M(CO)<inf>3</inf>Cp] (M = Mo or W) was used, the heterodinuclear products of monosubstitution [PtCl{M(CO)<inf>3</inf>Cp}{Ph<inf>2</inf>PN(R)PPh<inf>2</inf>-P,P}] (15 M = Mo, R = (CH<inf>2</inf>)<inf>5</inf>CH<inf>3</inf>; 16 M = Mo, R = CH<inf>2</inf>Ph; 17 M = W, R = (CH<inf>2</inf>)<inf>5</inf>CH<inf>3</inf>; 18 M = W, R = CH<inf>2</inf>Ph) were obtained, which are the precursors to the bicyclic products 3, 4, 9, and 10, respectively. Density functional calculations were performed to study the thermodynamics of the formation of all the new complexes, to evaluate the relative stabilities of the isomeric chelated and bridged forms, and to trace the mechanism of formation of the phosphanido-bridged products 3, 4, 9, and 10. It was concluded that Pt(II) complexes containing a thioether-functionalized short-bite ligand, [PtCl<inf>2</inf>{Ph<inf>2</inf>PN(R)PPh<inf>2</inf>}], react with Na[M(CO)<inf>3</inf>Cp] to yield first heterodinuclear Pt-M and then heterotrinuclear PtM<inf>2</inf> complexes resulting from the activation of a P-C bond in one of the PPh<inf>2</inf> groups and phenyl migration to Pt. The critical role of an intramolecular thioether group was demonstrated. (Chemical Equation Presented).
Sulfur-Assisted Phenyl Migration from Phosphorus to Platinum in PtW2 and PtMo2 Clusters Containing Thioether-Functionalized Short-Bite Ligands of the Bis(diphenylphosphanyl)amine-Type
The reactivity of dichloroplatinum(II) complexes containing thioether-functionalized bis(diphenylphosphanyl)amines of formula (Ph2P)2N(CH2)2SR (R = (CH2)5CH3, CH2Ph) toward group 6 carbonylmetalates Na[M(CO)3Cp] (M = Mo or W, Cp = cyclopentadienyl) was explored. Reactions with two or more equivalents of Na[M(CO)3Cp] (M = Mo or W) afforded the trinuclear complexes of general formula [PtPh{M(CO)3Cp}{?-P(Ph)N(CH2CH2SR)(PPh2)-?3P,P,S}M(CO)2Cp] (3 M = Mo, R = (CH2)5CH3; 4 M = Mo, R = CH2Ph; 9 M = W, R = (CH2)5CH3; 10 M = W, R = CH2Ph), the structure of which consists of a six-membered platinacycle condensed with a four-membered M-P-N-P cycle, together with small amounts of isomeric PtM2 clusters [PtM2(CO)5Cp2{(Ph2P)2N(CH2CH2SR)-?2P,P}] (5 M = Mo, R = (CH2)5CH3; 6 M = Mo, R = CH2Ph; 11 M = W, R = (CH2)5CH3; 12 M = W, R = CH2Ph) in which the ligand (Ph2P)2NR solely chelates the Pt atom or bridges an M-Pt bond as in [PtM2(CO)5Cp2{?-(Ph2P)2N(CH2CH2SR)-?2P,P}] (7 M = Mo, R = (CH2)5CH3; 8 M = Mo, R = CH2Ph; 13 M = W, R = (CH2)5CH3; 14 M = W, R = CH2Ph). The synthesis of the trinuclear complexes 3, 4, 9, and 10 entails an unexpected P-phenyl bond cleavage reaction and phenyl migration onto Pt. When only 1 equiv of Na[M(CO)3Cp] (M = Mo or W) was used, the heterodinuclear products of monosubstitution [PtCl{M(CO)3Cp}{Ph2PN(R)PPh2-P,P}] (15 M = Mo, R = (CH2)5CH3; 16 M = Mo, R = CH2Ph; 17 M = W, R = (CH2)5CH3; 18 M = W, R = CH2Ph) were obtained, which are the precursors to the bicyclic products 3, 4, 9, and 10, respectively. Density functional calculations were performed to study the thermodynamics of the formation of all the new complexes, to evaluate the relative stabilities of the isomeric chelated and bridged forms, and to trace the mechanism of formation of the phosphanido-bridged products 3, 4, 9, and 10. It was concluded that Pt(II) complexes containing a thioether-functionalized short-bite ligand, [PtCl2{Ph2PN(R)PPh2}], react with Na[M(CO)3Cp] to yield first heterodinuclear Pt-M and then heterotrinuclear PtM2 complexes resulting from the activation of a P-C bond in one of the PPh2 groups and phenyl migration to Pt. The critical role of an intramolecular thioether group was demonstrated. (Chemical Equation Presented).
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.14243/291950
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simulazione ASN
Il report seguente simula gli indicatori relativi alla propria produzione scientifica in relazione alle soglie ASN 2023-2025 del proprio SC/SSD. Si ricorda che il superamento dei valori soglia (almeno 2 su 3) è requisito necessario ma non sufficiente al conseguimento dell'abilitazione. La simulazione si basa sui dati IRIS e sugli indicatori bibliometrici alla data indicata e non tiene conto di eventuali periodi di congedo obbligatorio, che in sede di domanda ASN danno diritto a incrementi percentuali dei valori. La simulazione può differire dall'esito di un’eventuale domanda ASN sia per errori di catalogazione e/o dati mancanti in IRIS, sia per la variabilità dei dati bibliometrici nel tempo. Si consideri che Anvur calcola i valori degli indicatori all'ultima data utile per la presentazione delle domande.
La presente simulazione è stata realizzata sulla base delle specifiche raccolte sul tavolo ER del Focus Group IRIS coordinato dall'Università di Modena e Reggio Emilia e delle regole riportate nel DM 589/2018 e allegata Tabella A. Cineca, l'Università di Modena e Reggio Emilia e il Focus Group IRIS non si assumono alcuna responsabilità in merito all’uso che il diretto interessato o terzi faranno della simulazione. Si specifica inoltre che la simulazione contiene calcoli effettuati con dati e algoritmi di pubblico dominio e deve quindi essere considerata come un mero ausilio al calcolo svolgibile manualmente o con strumenti equivalenti.
