Silanol-based pincer Pt(II) complexes

Synthesis, structure, and unusual reactivity

Edward E. Korshin, Gregory Leitus, Linda J W Shimon, Leonid Konstantinovski, David Milstein

Research output: Contribution to journalArticle

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Abstract

Aiming at the generation of a silanone intramolecularly bound to platinum, we prepared pincer-type PSiP silanol Pt(II) complexes. While a stable silanone complex was not isolated, unusual reactivity modes, involving its possible intermediacy, were observed. Treatment of the new PSiH2P-type ligand (o-iPr2PC6H4)2SiH2 (7) with (Me2S)2Pt(Me)Cl yields the pincer-type hydrosilane complex [{(o- iPr2PC6H4)2SiH}PtCl] (8), which upon Ir(I)-catalyzed hydrolytic oxidation gives the structurally characterized silanol complex [{(o- iPr2PC6H 4)2SiOH}PtCl] (3). Complex 3, comprising in its structure the nucleophilic silanol fragment and electrophilic Pt(II)-Cl moiety, exhibits dual reactivity. Its reaction with the non-nucleophilic KB(C6F 5)4 in fluorobenzene leads to the ionic complex [{(o- iPr2PC6H4)2SiOH}Pt]+ [(C6F5)4B]- (9), which reacts with CO to yield the structurally characterized [{(o- iPr2PC 6H4)2SiOH}PtCO]+ [(C 6F5)4B]- (10). Treatment of 3 with non-nucleophilic bases leads to unprecedented rearrangement and coupling, resulting in the structurally characterized, unusual binuclear complex 11. The structure of 11 comprises two different fragments: the original O-Si-Pt(II)-Cl pattern, and the newly formed silanolate Pt(II)-H pattern, which are connected via a disiloxane bridge. Complex 9 undergoes a similar hydrolytic rearrangement in the presence of iPr2NEt to give the mononuclear silanolate Pt(II)-H complex 17. Both these rearrangement-coupling reactions probably involve the inner-sphere generation of an intermediate silanone 14, which undergoes nucleophilic attack by the starting silanol 3 to yield complex 11, or adds a water molecule to yield complex 17. X-ray diffraction studies of 3, 10, and 11 exhibit a very short Si-Pt bond length (2.27-2.28 Å) in the neutral complexes 3 and 11 that elongates to 2.365 Å in the carbonyl complex 10. A significantly compressed geometry of the silanolate platinum(II)-hydride fragment B of the binuclear complex 11 features a Pt(2)-O(2)-Si(2) angle of 100.4 (3)° and a remarkably short Pt(2)⋯Si(2) [2.884 (3) Å] distance.

Original languageEnglish
Pages (from-to)7177-7189
Number of pages13
JournalInorganic Chemistry
Volume47
Issue number16
DOIs
Publication statusPublished - Aug 18 2008

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reactivity
fragments
platinum
synthesis
Platinum
Fluorobenzenes
attack
hydrides
Bond length
Carbon Monoxide
Hydrides
ligands
oxidation
geometry
Ligands
diffraction
X ray diffraction
Oxidation
water
Molecules

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Silanol-based pincer Pt(II) complexes : Synthesis, structure, and unusual reactivity. / Korshin, Edward E.; Leitus, Gregory; Shimon, Linda J W; Konstantinovski, Leonid; Milstein, David.

In: Inorganic Chemistry, Vol. 47, No. 16, 18.08.2008, p. 7177-7189.

Research output: Contribution to journalArticle

Korshin, EE, Leitus, G, Shimon, LJW, Konstantinovski, L & Milstein, D 2008, 'Silanol-based pincer Pt(II) complexes: Synthesis, structure, and unusual reactivity', Inorganic Chemistry, vol. 47, no. 16, pp. 7177-7189. https://doi.org/10.1021/ic800457u
Korshin, Edward E. ; Leitus, Gregory ; Shimon, Linda J W ; Konstantinovski, Leonid ; Milstein, David. / Silanol-based pincer Pt(II) complexes : Synthesis, structure, and unusual reactivity. In: Inorganic Chemistry. 2008 ; Vol. 47, No. 16. pp. 7177-7189.
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abstract = "Aiming at the generation of a silanone intramolecularly bound to platinum, we prepared pincer-type PSiP silanol Pt(II) complexes. While a stable silanone complex was not isolated, unusual reactivity modes, involving its possible intermediacy, were observed. Treatment of the new PSiH2P-type ligand (o-iPr2PC6H4)2SiH2 (7) with (Me2S)2Pt(Me)Cl yields the pincer-type hydrosilane complex [{(o- iPr2PC6H4)2SiH}PtCl] (8), which upon Ir(I)-catalyzed hydrolytic oxidation gives the structurally characterized silanol complex [{(o- iPr2PC6H 4)2SiOH}PtCl] (3). Complex 3, comprising in its structure the nucleophilic silanol fragment and electrophilic Pt(II)-Cl moiety, exhibits dual reactivity. Its reaction with the non-nucleophilic KB(C6F 5)4 in fluorobenzene leads to the ionic complex [{(o- iPr2PC6H4)2SiOH}Pt]+ [(C6F5)4B]- (9), which reacts with CO to yield the structurally characterized [{(o- iPr2PC 6H4)2SiOH}PtCO]+ [(C 6F5)4B]- (10). Treatment of 3 with non-nucleophilic bases leads to unprecedented rearrangement and coupling, resulting in the structurally characterized, unusual binuclear complex 11. The structure of 11 comprises two different fragments: the original O-Si-Pt(II)-Cl pattern, and the newly formed silanolate Pt(II)-H pattern, which are connected via a disiloxane bridge. Complex 9 undergoes a similar hydrolytic rearrangement in the presence of iPr2NEt to give the mononuclear silanolate Pt(II)-H complex 17. Both these rearrangement-coupling reactions probably involve the inner-sphere generation of an intermediate silanone 14, which undergoes nucleophilic attack by the starting silanol 3 to yield complex 11, or adds a water molecule to yield complex 17. X-ray diffraction studies of 3, 10, and 11 exhibit a very short Si-Pt bond length (2.27-2.28 {\AA}) in the neutral complexes 3 and 11 that elongates to 2.365 {\AA} in the carbonyl complex 10. A significantly compressed geometry of the silanolate platinum(II)-hydride fragment B of the binuclear complex 11 features a Pt(2)-O(2)-Si(2) angle of 100.4 (3)° and a remarkably short Pt(2)⋯Si(2) [2.884 (3) {\AA}] distance.",
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AU - Milstein, David

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N2 - Aiming at the generation of a silanone intramolecularly bound to platinum, we prepared pincer-type PSiP silanol Pt(II) complexes. While a stable silanone complex was not isolated, unusual reactivity modes, involving its possible intermediacy, were observed. Treatment of the new PSiH2P-type ligand (o-iPr2PC6H4)2SiH2 (7) with (Me2S)2Pt(Me)Cl yields the pincer-type hydrosilane complex [{(o- iPr2PC6H4)2SiH}PtCl] (8), which upon Ir(I)-catalyzed hydrolytic oxidation gives the structurally characterized silanol complex [{(o- iPr2PC6H 4)2SiOH}PtCl] (3). Complex 3, comprising in its structure the nucleophilic silanol fragment and electrophilic Pt(II)-Cl moiety, exhibits dual reactivity. Its reaction with the non-nucleophilic KB(C6F 5)4 in fluorobenzene leads to the ionic complex [{(o- iPr2PC6H4)2SiOH}Pt]+ [(C6F5)4B]- (9), which reacts with CO to yield the structurally characterized [{(o- iPr2PC 6H4)2SiOH}PtCO]+ [(C 6F5)4B]- (10). Treatment of 3 with non-nucleophilic bases leads to unprecedented rearrangement and coupling, resulting in the structurally characterized, unusual binuclear complex 11. The structure of 11 comprises two different fragments: the original O-Si-Pt(II)-Cl pattern, and the newly formed silanolate Pt(II)-H pattern, which are connected via a disiloxane bridge. Complex 9 undergoes a similar hydrolytic rearrangement in the presence of iPr2NEt to give the mononuclear silanolate Pt(II)-H complex 17. Both these rearrangement-coupling reactions probably involve the inner-sphere generation of an intermediate silanone 14, which undergoes nucleophilic attack by the starting silanol 3 to yield complex 11, or adds a water molecule to yield complex 17. X-ray diffraction studies of 3, 10, and 11 exhibit a very short Si-Pt bond length (2.27-2.28 Å) in the neutral complexes 3 and 11 that elongates to 2.365 Å in the carbonyl complex 10. A significantly compressed geometry of the silanolate platinum(II)-hydride fragment B of the binuclear complex 11 features a Pt(2)-O(2)-Si(2) angle of 100.4 (3)° and a remarkably short Pt(2)⋯Si(2) [2.884 (3) Å] distance.

AB - Aiming at the generation of a silanone intramolecularly bound to platinum, we prepared pincer-type PSiP silanol Pt(II) complexes. While a stable silanone complex was not isolated, unusual reactivity modes, involving its possible intermediacy, were observed. Treatment of the new PSiH2P-type ligand (o-iPr2PC6H4)2SiH2 (7) with (Me2S)2Pt(Me)Cl yields the pincer-type hydrosilane complex [{(o- iPr2PC6H4)2SiH}PtCl] (8), which upon Ir(I)-catalyzed hydrolytic oxidation gives the structurally characterized silanol complex [{(o- iPr2PC6H 4)2SiOH}PtCl] (3). Complex 3, comprising in its structure the nucleophilic silanol fragment and electrophilic Pt(II)-Cl moiety, exhibits dual reactivity. Its reaction with the non-nucleophilic KB(C6F 5)4 in fluorobenzene leads to the ionic complex [{(o- iPr2PC6H4)2SiOH}Pt]+ [(C6F5)4B]- (9), which reacts with CO to yield the structurally characterized [{(o- iPr2PC 6H4)2SiOH}PtCO]+ [(C 6F5)4B]- (10). Treatment of 3 with non-nucleophilic bases leads to unprecedented rearrangement and coupling, resulting in the structurally characterized, unusual binuclear complex 11. The structure of 11 comprises two different fragments: the original O-Si-Pt(II)-Cl pattern, and the newly formed silanolate Pt(II)-H pattern, which are connected via a disiloxane bridge. Complex 9 undergoes a similar hydrolytic rearrangement in the presence of iPr2NEt to give the mononuclear silanolate Pt(II)-H complex 17. Both these rearrangement-coupling reactions probably involve the inner-sphere generation of an intermediate silanone 14, which undergoes nucleophilic attack by the starting silanol 3 to yield complex 11, or adds a water molecule to yield complex 17. X-ray diffraction studies of 3, 10, and 11 exhibit a very short Si-Pt bond length (2.27-2.28 Å) in the neutral complexes 3 and 11 that elongates to 2.365 Å in the carbonyl complex 10. A significantly compressed geometry of the silanolate platinum(II)-hydride fragment B of the binuclear complex 11 features a Pt(2)-O(2)-Si(2) angle of 100.4 (3)° and a remarkably short Pt(2)⋯Si(2) [2.884 (3) Å] distance.

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