Impact of the Novel Z-Acceptor Ligand Bis{(<i>ortho</i>-diphenylphosphino)phenyl}zinc (ZnPhos) on the Formation and Reactivity of Low-Coordinate Ru(0) Centers

Miloserdov, Fedor M.; Isaac, Connie J.; Beck, Madeleine L.; Burnage, Arron L.; Farmer, James C.; Macgregor, Stuart A.; Mahon, Mary F.; Whittlesey, Michael K.

doi:10.1021/acs.inorgchem.0c01683

Cited by 11 publications

(20 citation statements)

References 97 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Elemental analyses were performed by Elemental Microanalysis Ltd. (Okehampton, Devon, U.K.). Compounds 1 , 13 2 , 14 3 , 13 and IMes 57 were prepared according to literature methods.…”

Section: Methodsmentioning

confidence: 99%

“…In this particular case, both Ru and Zn centers are coordinatively unsaturated, and this “dual unsaturation” allows them to act cooperatively in the stoichiometric activation of H 2 to give IV . 12 We have interpreted Ru–Zn bonding within complex III and other related Ru–Zn complexes 13 , 14 in terms of a donor–acceptor interaction between a Ru(0) metal center and Z-type Zn-based acceptor ligands.…”

Section: Introductionmentioning

confidence: 99%

“… 12 − 14 , 19 − 21 Accordingly, the reaction of complex 1 with ZnMe 2 resulted in further alkane elimination and formation of neutral [RuZn 2 Me 2 ] complex 2 . 14 Alternatively, reaction with a source of [ZnMe] + induced C–H reductive coupling in 1 and formation of cationic [RuZn 2 Me 2 ] complex 3 . 13 …”

Section: Introductionmentioning

confidence: 99%

“…12−14,19−21 Accordingly, the reaction of complex 1 with ZnMe 2 resulted in further alkane elimination and formation of neutral [RuZn 2 Me 2 ] complex 2. 14 Alternatively, reaction with a source of [ZnMe] + induced C−H reductive coupling in 1 and formation of cationic [RuZn 2 Me 2 ] complex 3. 13 Another strategy for the preparation of [TM-Zn 2 R 2 ] species 23−25 involves addition of Carmona's Cp*Zn−ZnCp* dimer to low-valent precursors.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Complex III is formed upon elimination of an alkane, − an approach we have used to prepare other Ru and mono-Zn-containing products, including complex 1 in Scheme that features bridging hydride and aryl ligands. − ,− Accordingly, the reaction of complex 1 with ZnMe 2 resulted in further alkane elimination and formation of neutral [RuZn 2 Me 2 ] complex 2 . Alternatively, reaction with a source of [ZnMe] + induced C–H reductive coupling in 1 and formation of cationic [RuZn 2 Me 2 ] complex 3 …”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Bonding and Reactivity of a Pair of Neutral and Cationic Heterobimetallic RuZn₂ Complexes

et al. 2021

Self Cite

View full text Add to dashboard Cite

A combined experimental and computational study of the structure and reactivity of two [RuZn 2 Me 2 ] complexes, neutral [Ru(PPh 3 )(Ph 2 PC 6 H 4 ) 2 (ZnMe) 2 ] ( 2 ) and cationic [Ru(PPh 3 ) 2 (Ph 2 PC 6 H 4 )(ZnMe) 2 ][BAr F 4 ] ([BAr F 4 ] = [B{3,5-(CF 3 ) 2 C 6 H 3 } 4 ]) ( 3 ), is presented. Structural and computational analyses indicate these complexes are best formulated as containing discrete ZnMe ligands in which direct Ru–Zn bonding is complemented by weaker Zn···Zn interactions. The latter are stronger in 2 , and both complexes exhibit an additional Zn···C aryl interaction with a cyclometalated phosphine ligand, this being stronger in 3 . Both 2 and 3 show diverse reactivity under thermolysis and with Lewis bases (P n Bu 3 , PCy 3 , and IMes). With 3 , all three Lewis bases result in the loss of [ZnMe] + . In contrast, 2 undergoes PPh 3 substitution with P n Bu 3 , but with IMes, loss of ZnMe 2 occurs to form [Ru(PPh 3 )(C 6 H 4 PPh 2 )(C 6 H 4 PPhC 6 H 4 Zn(IMes))H] ( 7 ). The reaction of 3 with H 2 affords the cationic trihydride complex [Ru(PPh 3 ) 2 (ZnMe) 2 (H) 3 ][BAr F 4 ] ( 12 ). Computational analyses indicate that both 12 and 7 feature bridging hydrides that are biased toward Ru over Zn.

show abstract

“…Elemental analyses were performed by Elemental Microanalysis Ltd. (Okehampton, Devon, U.K.). Compounds 1 , 13 2 , 14 3 , 13 and IMes 57 were prepared according to literature methods.…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…12−14,19−21 Accordingly, the reaction of complex 1 with ZnMe 2 resulted in further alkane elimination and formation of neutral [RuZn 2 Me 2 ] complex 2. 14 Alternatively, reaction with a source of [ZnMe] + induced C−H reductive coupling in 1 and formation of cationic [RuZn 2 Me 2 ] complex 3. 13 Another strategy for the preparation of [TM-Zn 2 R 2 ] species 23−25 involves addition of Carmona's Cp*Zn−ZnCp* dimer to low-valent precursors.…”

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Bonding and Reactivity of a Pair of Neutral and Cationic Heterobimetallic RuZn₂ Complexes

et al. 2021

Self Cite

View full text Add to dashboard Cite

show abstract

Experimental and Computational Studies of Ruthenium Complexes Bearing Z-Acceptor Aluminum-Based Phosphine Pincer Ligands

et al. 2022

Self Cite

View full text Add to dashboard Cite

Reaction of [Ru(C6H4PPh2)2(Ph2PC6H4AlMe(THF))H] with CO results in clean conversion to the Ru−Al heterobimetallic complex [Ru(AlMePhos)(CO)3] (1), where AlMePhos is the novel P–Al(Me)–P pincer ligand (o-Ph2PC6H4)2AlMe. Under photolytic conditions, 1 reacts with H2 to give [Ru(AlMePhos)(CO)2(μ-H)H] (2) that is characterized by multinuclear NMR and IR spectroscopies. DFT calculations indicate that 2 features one terminal and one bridging hydride that are respectively anti and syn to the AlMe group. Calculations also define a mechanism for H2 addition to 1 and predict facile hydride exchange in 2 that is also observed experimentally. Reaction of 1 with B(C6F5)3 results in Me abstraction to form the ion pair [Ru(AlPhos)(CO)3][MeB(C6F5)3] (4) featuring a cationic [(o-Ph2PC6H4)2Al]+ ligand, [AlPhos]+. The Ru–Al distance in 4 (2.5334(16) Å) is significantly shorter than that in 1 (2.6578(6) Å), consistent with an enhanced Lewis acidity of the [AlPhos]+ ligand. This is corroborated by a blue shift in both the observed and computed νCO stretching frequencies upon Me abstraction. Electronic structure analyses (QTAIM and EDA-ETS) comparing 1, 4, and the previously reported [Ru(ZnPhos)(CO)3] analogue (ZnPhos = (o-Ph2PC6H4)2Zn) indicate that the Lewis acidity of these pincer ligands increases along the series ZnPhos < AlMePhos < [AlPhos]+.

show abstract

Isolobal Cationic Iridium Dihydride and Dizinc Complexes: A Dual Role for the ZnR Ligand Enhances H₂ Activation

Walsh,

Sotorrios,

Cameron

et al. 2024

Inorg. Chem.

View full text Add to dashboard Cite

The reaction of [Ir(IPr) 2 H 2 ][BAr F 4 ] (1; IPr = 1,3bis(2,6-diisopropylphenyl)imidazol-2-ylidene; BAr F 4 = B-{C 6 H 3 (3,5-CF 3 ) 2 } 4 ) with ZnMe 2 proceeds with CH 4 elimination to give [Ir(IPr)(IPr′)(ZnMe) 2 H][BAr F 4 ] (3, where (IPr′) is a cyclometalated IPr ligand). 3 reacts with H 2 to form tetrahydride [Ir(IPr) 2 (ZnMe) 2 H 4 ][BAr F 4 ], 4, that loses H 2 under forcing conditions to form [Ir(IPr) 2 (ZnMe) 2 H 2 ][BAr F 4 ], 5. Crystallization of 3 also results in the formation of its noncyclometalated isomer, [Ir(IPr) 2 (ZnMe) 2 ][BAr F 4 ], 2, in the solid state. Reactions of 1 and CdMe 2 form [Ir(IPr) 2 (CdMe) 2 ][BAr F 4 ], 6, and [Ir(IPr)(IPr′)-(CdMe) 2 H][BAr F 4 ], 7, which reacts with H 2 to give [Ir-(IPr) 2 (CdMe) 2 H 4 ][BAr F 4 ], 8, and [Ir(IPr) 2 (CdMe) 2 H 2 ][BAr F 4 ], 9. Structures of 2−8 are determined crystallographically. Computational analyses show the various hydrides in 3−5 sit on a terminal to bridging continuum, with bridging hydrides exhibiting greater Zn δ+ •••H δ− electrostatic interaction. The isolobal analogy between H and ZnMe ligands holds when both are present as terminal ligands. However, the electrostatic component to the Zn δ+ •••H δ− unit renders it significantly different to a nominally isolobal H•••H moiety. Thus, H 2 addition to 3 is irreversible, whereas H 2 addition to 1 reversibly forms highly fluxional [Ir(IPr) 2 (η 2 -H 2 ) 2 H 2 ][BAr F 4 ], 11. Computed mechanisms for cyclometalation and H 2 addition showcase the role of the bridging Zn δ+ •••H δ− moiety in promoting reactivity. In this, the Lewis acidic ZnMe ligand plays a dual role: as a terminal Z-type ligand that can stabilize electron-rich Ir centers through direct Ir-ZnMe bonding, or by stabilizing strongly hydridic character via Zn δ+ •••H δ− interactions.

show abstract

Impact of the Novel Z-Acceptor Ligand Bis{(ortho-diphenylphosphino)phenyl}zinc (ZnPhos) on the Formation and Reactivity of Low-Coordinate Ru(0) Centers

Cited by 11 publications

References 97 publications

Bonding and Reactivity of a Pair of Neutral and Cationic Heterobimetallic RuZn₂ Complexes

Bonding and Reactivity of a Pair of Neutral and Cationic Heterobimetallic RuZn₂ Complexes

Experimental and Computational Studies of Ruthenium Complexes Bearing Z-Acceptor Aluminum-Based Phosphine Pincer Ligands

Isolobal Cationic Iridium Dihydride and Dizinc Complexes: A Dual Role for the ZnR Ligand Enhances H₂ Activation

Contact Info

Product

Resources

About

Impact of the Novel Z-Acceptor Ligand Bis{(ortho-diphenylphosphino)phenyl}zinc (ZnPhos) on the Formation and Reactivity of Low-Coordinate Ru(0) Centers

Cited by 11 publications

References 97 publications

Bonding and Reactivity of a Pair of Neutral and Cationic Heterobimetallic RuZn2 Complexes

Bonding and Reactivity of a Pair of Neutral and Cationic Heterobimetallic RuZn2 Complexes

Experimental and Computational Studies of Ruthenium Complexes Bearing Z-Acceptor Aluminum-Based Phosphine Pincer Ligands

Isolobal Cationic Iridium Dihydride and Dizinc Complexes: A Dual Role for the ZnR Ligand Enhances H2 Activation

Contact Info

Product

Resources

About

Bonding and Reactivity of a Pair of Neutral and Cationic Heterobimetallic RuZn₂ Complexes

Bonding and Reactivity of a Pair of Neutral and Cationic Heterobimetallic RuZn₂ Complexes

Isolobal Cationic Iridium Dihydride and Dizinc Complexes: A Dual Role for the ZnR Ligand Enhances H₂ Activation