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A T-shape diphosphinoborane palladium(0) complex

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ABSTRACT

Cydpbphcydpbph9: The reaction of CpPd(η3-C3H5) with the new diphosphinoborane ligand derivative (o-PCy2-C6H4)2BPh affords the T-shape complex ()Pd(0) , which was characterized by X-ray analysis.

No MeSH data available.


Thermal ellipsoid plots of complex 9 at the 50% probability level. H atoms and one molecule of hexane have been omitted for clarity. Selected interatomic distances (Å) and angles (°): Pd1–B1 2.243(2), Pd1–P1 2.2761(6), Pd1–P2 2.3084(6), B1–Pd1–P1 85.82(6), B1–Pd1–P2 82.49(6), P1–Pd1–P2 157.72(2), C15–B1–C20 110.94(18), C15–B1–C35 116.58(18), C20–B1–C35 112.56(18).
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Figure 2: Thermal ellipsoid plots of complex 9 at the 50% probability level. H atoms and one molecule of hexane have been omitted for clarity. Selected interatomic distances (Å) and angles (°): Pd1–B1 2.243(2), Pd1–P1 2.2761(6), Pd1–P2 2.3084(6), B1–Pd1–P1 85.82(6), B1–Pd1–P2 82.49(6), P1–Pd1–P2 157.72(2), C15–B1–C20 110.94(18), C15–B1–C35 116.58(18), C20–B1–C35 112.56(18).

Mentions: CyDPBPh was reacted with 1 equiv of CpPd(η3-C3H5) in benzene. Complete conversion towards complex 9 with equimolar formation of 5-allylcyclopenta-1,3-diene was reached within 18 h at 50 °C. Complex 9 showed a singlet resonance at δ 41.0 in the 31P NMR spectrum and a broad resonance at δ 22 (w1/2 = 800 ± 50 Hz) in the 11B NMR spectrum. High field shift and narrowing of the 11B NMR with respect to the free CyDPBPh ligand indicated the presence of a strong dative Pd(0)→B bond [7]. Despite the absence of a stabilizing co-ligand, we found complex 9 to be very stable in solution. The coordinating properties of CyDPBPh deviate from those observed for its aryl derivatives (PhDPBPh ((o-PPh2-C6H4)2BPh) and PhDPBMes ((o-PPh2-C6H4)2B(Mes))). For these ligands the reaction with one equivalent of CpPd(η3-C3H5) leads to 50% consumption of CpPd(η3-C3H5) with simultaneous formation of 5-allylcyclopenta-1,3-diene, but complete conversion of the ligand pointing towards the formation of a bisligand complex (DPB)2Pd [7]. Unlike complex 2 we were unable to form a pyridine adduct complex by treatment of 9 with 10 equiv of pyridine. Single crystals of complex 9 suitable for X-ray diffraction analysis were grown from hexane (Fig. 2).


A T-shape diphosphinoborane palladium(0) complex
Thermal ellipsoid plots of complex 9 at the 50% probability level. H atoms and one molecule of hexane have been omitted for clarity. Selected interatomic distances (Å) and angles (°): Pd1–B1 2.243(2), Pd1–P1 2.2761(6), Pd1–P2 2.3084(6), B1–Pd1–P1 85.82(6), B1–Pd1–P2 82.49(6), P1–Pd1–P2 157.72(2), C15–B1–C20 110.94(18), C15–B1–C35 116.58(18), C20–B1–C35 112.56(18).
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Figure 2: Thermal ellipsoid plots of complex 9 at the 50% probability level. H atoms and one molecule of hexane have been omitted for clarity. Selected interatomic distances (Å) and angles (°): Pd1–B1 2.243(2), Pd1–P1 2.2761(6), Pd1–P2 2.3084(6), B1–Pd1–P1 85.82(6), B1–Pd1–P2 82.49(6), P1–Pd1–P2 157.72(2), C15–B1–C20 110.94(18), C15–B1–C35 116.58(18), C20–B1–C35 112.56(18).
Mentions: CyDPBPh was reacted with 1 equiv of CpPd(η3-C3H5) in benzene. Complete conversion towards complex 9 with equimolar formation of 5-allylcyclopenta-1,3-diene was reached within 18 h at 50 °C. Complex 9 showed a singlet resonance at δ 41.0 in the 31P NMR spectrum and a broad resonance at δ 22 (w1/2 = 800 ± 50 Hz) in the 11B NMR spectrum. High field shift and narrowing of the 11B NMR with respect to the free CyDPBPh ligand indicated the presence of a strong dative Pd(0)→B bond [7]. Despite the absence of a stabilizing co-ligand, we found complex 9 to be very stable in solution. The coordinating properties of CyDPBPh deviate from those observed for its aryl derivatives (PhDPBPh ((o-PPh2-C6H4)2BPh) and PhDPBMes ((o-PPh2-C6H4)2B(Mes))). For these ligands the reaction with one equivalent of CpPd(η3-C3H5) leads to 50% consumption of CpPd(η3-C3H5) with simultaneous formation of 5-allylcyclopenta-1,3-diene, but complete conversion of the ligand pointing towards the formation of a bisligand complex (DPB)2Pd [7]. Unlike complex 2 we were unable to form a pyridine adduct complex by treatment of 9 with 10 equiv of pyridine. Single crystals of complex 9 suitable for X-ray diffraction analysis were grown from hexane (Fig. 2).

View Article: PubMed Central - HTML - PubMed

ABSTRACT

Cydpbphcydpbph9: The reaction of CpPd(η3-C3H5) with the new diphosphinoborane ligand derivative (o-PCy2-C6H4)2BPh affords the T-shape complex ()Pd(0) , which was characterized by X-ray analysis.

No MeSH data available.