Interaction between d- and p-block metals: Synthesis and structure of platinum-alane adducts
Interaction between d- and p-block metals: Synthesis and structure of platinum-alane adducts
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DOI：
10.1002/anie.200702726
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发表时间：
2007-01-01
影响因子：
16.6
通讯作者：
Radacki, Krzysztof
中科院分区：
文献类型：
--
作者：
Braunschweig, Holger;Gruss, Katrin;Radacki, Krzysztof
过渡金属和典型的Lewis酸BF3之间的配位键早在1966年就被提出[1]，但在30年后受到质疑。[2]然而，Hill，[3]Parkin，[4]Bourissou，[5]和Rabinovich[6]以及各自的同事最近的工作表明，[LNM±BR3][7]类型的硼烷络合物可以从一系列晚期Lewis碱性过渡金属中获得，而配位键的性质已经通过实验和计算研究得到了阐明。此外，金属-膦碎片{M(PCy3)}(M=Pd，Pt)已被证明是一系列配位的硼基[8]和亚丁烯配体的多功能金属碱。[9]较重的第13族元素也已知形成各种过渡金属络合物，类似于硼。[10]尽管存在过多具有过渡金属-铝键的络合物，但相应的丙烷络合物[LNM±AlR3]非常罕见。据我们所知，无支撑的过渡金属铝键的结构证据仅限于离子物种[Net 4][(η5-C5H5)(OC)2Fe±AlPh 3]。[11]Bergman和他的同事报道了[(η5-C5Me 5)(Me3P)IrH2(AlPh)]的合成，根据结构数据，它有一定的Ir-Al相互作用。然而，这种金属-金属键是由两个桥接的氢原子支持的。[12]考虑到零价铂有明显的倾向于添加到三配位的硼中心，我们开始了研究，以将这种化学扩展到更高的同系物，铝。在这里，我们报道了第一个中性丙烷络合物，其中没有支承的配位键。用31P{1H}核磁共振研究了AlCl3与等摩尔量的[Pt(PCy3)2](1)在C6D6中的反应。在d=53.5ppm(1JPtP=3032赫兹)处观察到一个新的共振，它仅比1(d=62.3ppm，1JPtP=4161赫兹)略有前移。[13]Pt0物种与BCl3或其他卤化硼之间的相应反应通常是通过将硼-卤键氧化加成到铂中心进行的，伴随着31P{1H}核磁共振光谱共振的显著前场移动。[14]因此，观察到的化学位移
Dative bonds between transition metals and the archetypal Lewis acid BF3 were proposed as early as 1966,[1] but were called into question 30 years later.[2] However, more recent work by Hill,[3] Parkin,[4] Bourissou,[5] and Rabinovich [6] and respective co-workers has demonstrated that borane complexes of the type [LnMÀBR3][7] can be obtained from a range of late Lewis basic transition metals, and the nature of the dative metal–boron bond has been elucidated by experimental and computational studies. In addition, the metal–phosphine fragments {M (PCy3)}(M= Pd, Pt) have proven to act as versatile metal bases towards a range of coordinated boryl [8] and borylene ligands.[9]The heavier Group 13 elements are also known to form a variety of transition-metal complexes, in analogy to boron.[10] Despite the plethora of complexes with transition-metal–aluminum bonds, however, corresponding alane complexes [LnMÀAlR3] are exceptionally rare. Structural evidence for an unsupported dative transition-metal–aluminum bond is to our knowledge restricted to the ionic species [NEt4][(η5-C5H5)(OC) 2FeÀAlPh3].[11] Bergman and co-workers reported the synthesis of [(η5-C5Me5)(Me3P) IrH2 (AlPh3)], which, according to structural data, has a certain amount of Ir–Al interaction. This metal–metal bond, however, is supported by two bridging hydrogen atoms.[12] Given the pronounced propensity of zerovalent platinum to add to three-coordinate boron centers, we initiated studies to extend this chemistry to the higher homologue, aluminum. Herein we report the first neutral alane complexes with an unsupported dative bond. The reaction of AlCl3 with an equimolar amount of [Pt (PCy3) 2](1) in C6D6 was monitored by 31P {1H} NMR spectroscopy. A new resonance at d= 53.5 ppm (1JPtP= 3032 Hz) was observed that is shifted only marginally upfield with respect to that of 1 (d= 62.3 ppm, 1JPtP= 4161 Hz).[13] Corresponding reactions between Pt0 species and BCl3 or other boron halides usually proceed by oxidative addition of the boron–halogen bond to the platinum center, which is accompanied by a significant upfield shift of the 31P {1H} NMR spectroscopic resonances.[14] Thus, the chemical shift observed