Proton‐Induced Change of the Coordination Mode of a Boron Group: Boryl Complexes [Mn(CO)4(PR3)(BH2⋅PMe3)] and Cationic Borane σ Complexes [Mn(CO)4(PR3)(η1‐BH3⋅PMe3)]+

Yasue, Takahiro; Kawano, Yukio; Shimoi, Mamoru

doi:10.1002/anie.200219992

Cited by 75 publications

(16 citation statements)

References 24 publications

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“…The average Mn⋅⋅⋅B distance (2.143 Å) and Mn−N bond length (2.052 Å) in 7 a , 8 a , and 8 b are similar to those in 1 and other related species . The average Mn−P bond length (2.257 Å) in 7 a , 8 a , and 8 b is shorter than that in [Mn(CO) 4 (PPhMe 2 )(BH 2 ⋅ PMe 3 )] (2.302(1) Å) …”

Section: Resultsmentioning

confidence: 67%

“…[12c, 26c, 27] The average MnÀPb ond length (2.257 )i n7a, 8a,a nd 8b is shorter than that in [Mn(CO) 4 (PPhMe 2 )(BH 2 ·PMe 3 )] (2.302 (1) ). [33] The 11 BNMR spectra of 7a, 7b, 8a,a nd 8b display very close chemical shifts (d = 18-23 ppm).C onsidering the molecular formula, the geometry,a nd the chemical shift values, 7a/ 7b and 8a/8b can be considered as isomers. Similar behavior was observedw hen 8-aminoquinoline and 2-aminopyridine ligands weret reated with metal precursors.…”

Section: Reactivity Of 1a Nd 3with Phosphinesmentioning

confidence: 99%

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Design, Synthesis, and Chemistry of Bis(σ)borate and Agostic Complexes of Group 7 Metals

Saha

Ramalakshmi

Gomosta

et al. 2017

Chemistry A European J

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A series of new bis(σ)borate and agostic complexes of group 7 metals have been synthesized and structurally characterized from various borate ligands, such as trihydrobis(benzothiazol-2-yl)amideborate (Na[(H B)bbza]), trihydro(2-aminobenzothiazolyl)borate (Na[(H B)abz]), and dihydrobis(2-mercaptopyridyl)borate (Na[(H B)mp ]) (bbza=bis(benzothiazol-2-yl)amine, abz=2-aminobenzothiazolyl, and mp=2-mercaptopyridyl). Photolysis of [Mn (CO) ] with Na[(H B)bbza] formed bis(σ)borate complex [Mn(CO) (μ-H) BHNCSC H (NR)] (1; R=NCSC H ). Octahedral complex [Re(CO) (N C S C H ) ] (2) was generated under similar reaction conditions with [Re (CO) ]. Similarly, when [Mn (CO) ] was treated with Na[(H B)abz], bis(σ)borate complex [Mn(CO) (μ-H) BH(HN CSC H )] (3) and the agostic complex [Mn(CO) (μ-H)BH(HN CSC H ) ] (4) were formed. To probe the potential formation of agostic complexes of the heavier group 7 metals, we carried out the photolysis of [M (CO) ] with Na[(H B)mp ] and found that [M(CO) (μ-H)BH(C H NS) ] (5: M=Re; 6: M=Mn) was formed in moderate yield. Complexes 1 and 3 feature a (κ -H,H,N) coordination mode, whereas 4, 5, and 6 display both (κ -H,N,N) and (κ -H,S,S) modes of the corresponding ligands. To investigate the lability of the CO ligands of 1 and 3, we treated the complexes with phosphine ligands that generated novel bis(σ)borate complexes [Mn(μ-H) (BHNCSC H )(NR)(CO) PL L'] (R=NCSC H ; 7 a: L=L'=Ph; 7 b: L=Ph, L'=Me) and [Mn(μ-H) BHN(NCSC H )R(CO) PL L'] (R=NCSC H ; 8 a: L=L'=Ph; 8 b: L=Ph, L'=Me). Complexes 7 and 8 are structural isomers with different coordination modes of the bbza ligand. In addition, DFT calculations were performed to shed some light on the bonding and electronic structures of these complexes.

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Section: Resultsmentioning

confidence: 67%

Section: Reactivity Of 1a Nd 3with Phosphinesmentioning

confidence: 99%

Design, Synthesis, and Chemistry of Bis(σ)borate and Agostic Complexes of Group 7 Metals

Saha

Ramalakshmi

Gomosta

et al. 2017

Chemistry A European J

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“…Der gebildete η 1 ‐koordinierte Hydrido‐Phosphino‐Boran‐Komplex 2 reagiert jedoch bereitwillig mit einem zweiten Äquivalent Kohlenmonoxid unter Wassserstoff‐Eliminierung und Bildung des Phosphan‐stabilisierten Boryl‐Komplexes 3 . Da Phosphino‐Borane deprotonierbar sind, scheint die Protonierung des Eisen‐Hydrids in 2 durch das η 1 ‐koordinierte Phosphino‐Boran im vorliegenden Fall ein möglicher Reaktionsweg zur Wasserstoff‐Eliminierung zu sein. Komplex 3 ist in Lösung nur bedingt stabil und isomerisiert langsam zu Komplex 1 .…”

Section: Methodsunclassified

Phosphan‐stabilisierte Borylene und Boryl‐Anionen als Liganden? Redoxaktivität in Bor‐basierten Pinzetten‐Komplexen

et al. 2016

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Stabilisierte Borylene (L 2 BHD)m it schwach p-akzeptierenden Substituenten L, wie Phosphanen, galten bisher als instabil. Hier beschreiben wir eine Serie von Komplexen, die formal ein Phosphan-stabilisiertes Borylen oder Boryl-Anion als Liganden enthalten. Im Unterschied zu gängigen dreibindigen Bor-Verbindungen agieren die hier beschriebenen Liganden als elektronendonierende Liganden. Die erhaltenen Eisen-Hydrid-Komplexe weisen eine ungewçhnliche Reaktivitäta uf und reagieren reversibel unter reduktiver B-H-Eliminierung,d ie formal mit einer Oxidation der Bor(I)-Donorgruppe einhergeht.

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“…The reverse reactionf rom ap hosphine-stabilized boryl complex of type C to a h 1 -phosphine-borane complex of type B can be induced by proton addition, as reportedf or the manganese complexes [Mn(CO) 4 (PR 3 )(BH 2 ·PMe 3 )] (PR 3 = PMe 2 Ph, PEt 3 )b yS himoi and co-workers. [15] Alternative reaction pathways of h 1 -phosphine-boranes B are assumed reaction steps in the dehydrocoupling of phosphine-boranes. [14,16] The BÀHa ctivation and concomitantP ÀBc ouplingo fah 1 -phosphineborane (type B)t oab is(phosphine)boronium or -borate complex was proposed by Manners and co-workerso nt he basis of DFT calculations for the [CpFe(CO) 2 {HP(BH 3 )Ph}]-catalyzed dehydropolymerization of phosphine-boranes.…”

Section: Introductionmentioning

confidence: 99%

“…In these reactions, formation of a phosphine‐stabilized boryl complex of type C was observed, which was formed by loss of H 2 from an η 1 ‐phosphine‐borane complex of type B (with a hydrido ligand as internal base). The reverse reaction from a phosphine‐stabilized boryl complex of type C to a η 1 ‐phosphine‐borane complex of type B can be induced by proton addition, as reported for the manganese complexes [Mn(CO) 4 (PR 3 )(BH 2 ⋅ PMe 3 )] (PR 3 =PMe 2 Ph, PEt 3 ) by Shimoi and co‐workers . Alternative reaction pathways of η 1 ‐phosphine‐boranes B are assumed reaction steps in the dehydrocoupling of phosphine‐boranes .…”

Section: Introductionmentioning

confidence: 99%

Umpolung at Boron: Ancillary‐Ligand‐Induced Formation of Boron‐Based Donor Ligands from Phosphine‐Boranes

Vondung

Alig

Ballmann

et al. 2018

Chemistry A European J

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Easy-to-prepare η -coordinated phosphine-borane ligands are demonstrated to liberate hydrogen upon treatment with different σ-donor/π-acceptor ligands (CO, tBuNC, CN ). Depending on the utilized ancillary ligand, different reaction pathways are observed, ranging from simple hydride protonation to iron-boron bond formation and subsequent rearrangement to pincer-type ligands based on a tricoordinate boron centre. The last-named reactivity is in line with a formal umpolung at the boron centre from a Lewis acidic borane to a Lewis basic boron-based donor ligand.

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Proton‐Induced Change of the Coordination Mode of a Boron Group: Boryl Complexes [Mn(CO)₄(PR₃)(BH₂⋅PMe₃)] and Cationic Borane σ Complexes [Mn(CO)₄(PR₃)(η¹‐BH₃⋅PMe₃)]⁺

Cited by 75 publications

References 24 publications

Design, Synthesis, and Chemistry of Bis(σ)borate and Agostic Complexes of Group 7 Metals

Design, Synthesis, and Chemistry of Bis(σ)borate and Agostic Complexes of Group 7 Metals

Phosphan‐stabilisierte Borylene und Boryl‐Anionen als Liganden? Redoxaktivität in Bor‐basierten Pinzetten‐Komplexen

Umpolung at Boron: Ancillary‐Ligand‐Induced Formation of Boron‐Based Donor Ligands from Phosphine‐Boranes

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