A new nickel diphosphine catalyst has been synthesized in which the bidentate ligand has two different phosphine donors, a typical PPh 2 group and a stronger σ-donating PEt 2 group. The catalyst was highly effective for the chain-growth polymerization of a 3-alkylthiophene monomer using a Suzuki–Miyaura cross-coupling. The catalyst is particularly effective for this polymerization in the presence of excess free ligand. The unsymmetrical diphosphine nickel complex reported here represents a new approach to tuning metal-ligand reactivity in the chain-growth polymerization of aromatic monomers. In addition, this new nickel catalyst exhibited increased hydrolytic resistance in the polymerization as compared to commercially available 1,3-bis(diphenylphosphino)propane nickel dichloride. A new nickel diphosphine catalyst was synthesized and evaluated for Suzuki–Miyaura cross-coupling polymerization. The diphosphine is comprised of two electronically and sterically distinct phosphine donors, a PPh 2 group and a PEt 2 group. The catalyst was employed to bring about controlled polymerization of a 3-hexylthiophene monomer to afford poly(3-hexylthiophene). The catalyst was particularly effective for bringing about this polymerization in the presence of excess free ligand. The catalyst resting state was also probed using NMR spectroscopy and an externally initiated catalyst.

中文翻译：

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用于催化剂转移聚合的具有不对称丙基桥连二膦配体的坚固镍催化剂

合成了一种新的二膦镍催化剂，其中二齿配体具有两个不同的膦供体，一个典型的 PPh 2 基团和一个更强的 σ 供体 PEt 2 基团。该催化剂对于使用 Suzuki-Miyaura 交叉偶联的 3-烷基噻吩单体的链增长聚合非常有效。该催化剂对于在过量游离配体存在下的聚合特别有效。此处报道的不对称二膦镍配合物代表了一种在芳族单体的链增长聚合中调节金属-配体反应性的新方法。此外，与市售的 1,3-双（二苯基膦基）丙烷二氯化镍相比，这种新型镍催化剂在聚合过程中表现出更高的耐水解性。合成并评估了一种新的二膦镍催化剂，用于 Suzuki-Miyaura 交叉偶联聚合反应。二膦由两个电子和空间上不同的膦供体、PPh 2 基团和PEt 2 基团组成。该催化剂用于引起3-己基噻吩单体的受控聚合以提供聚(3-己基噻吩)。该催化剂对于在过量游离配体存在下引起这种聚合特别有效。还使用核磁共振光谱和外部引发的催化剂探测了催化剂的静止状态。该催化剂用于引起3-己基噻吩单体的受控聚合以提供聚(3-己基噻吩)。该催化剂对于在过量游离配体存在下引起这种聚合特别有效。还使用核磁共振光谱和外部引发的催化剂探测了催化剂的静止状态。该催化剂用于引起3-己基噻吩单体的受控聚合以提供聚(3-己基噻吩)。该催化剂对于在过量游离配体存在下引起这种聚合特别有效。还使用核磁共振光谱和外部引发的催化剂探测了催化剂的静止状态。