普紹平1，閆革新1， 侯 英2
( 1. 昆明貴金屬研究所 國家貴金屬材料工程技術(shù)研究中心，
昆明 650221;
2. 云南瑞升科技有限公司， 昆明 650106)
摘 要: 合成了乙酰丙酮銠， 并采用紫外、 紅外、 核磁和質(zhì)譜等手段研究了乙酰丙酮銠(Ⅲ)的化學(xué)結(jié)構(gòu)特征。 結(jié)果表明： 乙酰丙酮銠屬于低自旋的惰性配合物； 由于配合物中離域π鍵的形成， 配體羰基已不具備典型的羰基特征； 在快原子的轟擊下， 乙酰丙酮銠的配位鍵逐一斷裂， 釋放出游離的乙酰丙酮， 最后形成103Rh+， 同時(shí)伴隨共價(jià)鍵的斷裂與重排； 在磁場(chǎng)中， 由于Rh3+的強(qiáng)吸電子效應(yīng)以及螯合環(huán)的環(huán)電子流效應(yīng)， H核化學(xué)位移向低場(chǎng)移動(dòng)。 通過TG-DTA和GC-MS分析并探討了乙酰丙酮銠的熱分解行為， 為其應(yīng)用提供了熱學(xué)依據(jù)和理論參考， 并建議以300 ℃作為以乙酰丙酮銠為前驅(qū)體的CVD銠沉積工藝的沉積溫度。
關(guān)鍵字: 乙酰丙酮銠; 結(jié)構(gòu)特征; 熱分解; 化學(xué)氣相沉積
PU Shao-ping1， YAN Ge-xin1, HOU Ying2
（ 1. National Engineering Research Center of Precious Metal,
Kunming Institute of Precious Metals, Kunming 650221, China;
2. Yunnan Reascend Science and Technology Co. LTD, Kunming 650221, China）
Abstract: Rhodium(Ⅲ) acetylacetonate ［Rh(acac)3］, a precursor for preparing Rh layers by CVD technique, was prepared. Its spectroscopic properties were investigated via UV-vis, IR, 1HNMR and MS and its thermal decomposition behavior via TG-DTA and GC-MS. The results show that,
Rh(acac)3 is a low spinning and inert coordination compound, the characteristics of carbonyls in the ligand disappear due to the formation of conjugate π bonds in
Rh3+—acac- chelating ring, after bombarded by fast atoms, the coordination bonds break and the organic covalent bonds are splited with the formation of 103Rh+, chemical shifts of H nuclei go downward to low field because of electron-attraction of Rh3+ and electron-cyclic effect in the chelating rings, and it sublimates and decomposes at 247 ℃ and 245 ℃ in air and argon, respectively. Series of new complexes, different with the temperatures, appear in the course of the decomposition, according to which it is suggested that a better deposit temperature should be 300 ℃ when plating Rh layers via CVD technique with Rh(acac)3 as the precursor.
Key words: rhodium(Ⅲ) acetylacetonate; chemical structure; thermal properties; CVD
