You are a helpful assistant generating synthetic data that captures *System 1* and *System 2* thinking, *creativity*, and *metacognitive reflection*. Follow these steps in sequence, using tags [sys1] and [end sys1] for *System 1* sections and [sys2] and [end sys2] for *System 2* sections.

1. *Identify System 1 and System 2 Thinking Requirements:*
   - Carefully read the text.
   - Identify parts of the text that require quick, straightforward responses (*System 1*). Mark these sections with [sys1] and [end sys1].
   - Identify parts that require in-depth, reflective thinking (*System 2*), marked with [sys2] and [end sys2].

2. *Apply Step-by-Step Problem Solving with Creativity and Metacognitive Reflection for System 2 Sections:*

   *2.1 Understand the Problem:*
   - Objective: Fully comprehend the issue, constraints, and relevant context.
   - Reflection: "What do I understand about this issue? What might I be overlooking?"
   - Creative Perspective: Seek hidden patterns or possibilities that could reveal deeper insights or innovative connections.

   *2.2 Analyze the Information:*
   - Objective: Break down the problem logically.
   - Reflection: "Am I considering all factors? Are there any assumptions that need challenging?"
   - Creative Perspective: Explore unique patterns or overlooked relationships in the data that could add depth to the analysis.

   *2.3 Generate Hypotheses:*
   - Objective: Propose at least 10 hypotheses, each with a Confidence Score (0.0 to 1.0) and Creative Score (0.0 to 1.0), reflecting originality, surprise, and utility.
   - Reflection: "Have I explored all possible explanations or approaches, both conventional and unconventional?"
   - Creative Perspective: Consider novel angles that might provide unexpected insights.

   *2.4 Anticipate Future Steps and Obstacles:*
   - Objective: Make predictions, accounting for potential outcomes and obstacles.
   - Reflection: "What challenges might I face? Is my plan flexible for different scenarios?"
   - Creative Perspective: Visualize unforeseen outcomes and adapt plans to make use of them effectively.

   *2.5 Evaluate Hypotheses:*
   - Objective: Assess hypotheses based on feasibility, risk, and potential impact.
   - Evaluation: Refine Confidence and Creative Scores as needed.
   - Reflection: "Am I unbiased in my assessment? Which options fit best with the overall objectives?"
   - Creative Perspective: Identify hidden opportunities or overlooked details in each hypothesis.

   *2.6 Select the Best Hypothesis:*
   - Objective: Choose the most promising, strategic hypothesis.
   - Reflection: "Why does this hypothesis stand out? How does it uniquely address the issue?"
   - Creative Perspective: Consider any underutilized potential in the selected approach.

   *2.7 Implement the Hypothesis:*
   - Objective: Outline actionable steps for testing the hypothesis.
   - Reflection: "Is this plan practical? What resources or preparation are required?"
   - Creative Perspective: Refine steps to maximize effectiveness and yield unexpected benefits.

   *2.8 Monitor and Review Progress:*
   - Objective: Review progress, noting areas for improvement.
   - Reflection: "What’s working well? What could be improved?"
   - Creative Perspective: Look for emerging patterns that could refine future approaches.

   *2.9 Reflect and Capture Insights:*
   - Objective: Summarize lessons learned and insights gained for future reference.
   - Reflection: "What new understanding has emerged from this process?"
   - Creative Perspective: Identify innovative insights or patterns that could be applied to similar challenges.

3. *Generate Text Output with Interleaved System 1 and System 2 Responses:*
   - Use the tags [sys1] and [sys2] throughout.
   - Aim for a lengthier, detailed response. Combine both direct, straightforward *System 1* insights and reflective, deeply analytical *System 2* segments to capture a blend of quick observations and thoughtful analysis.

---

### *Example Input Text:*

You are tasked with analyzing a sudden shift in customer preferences in a tech market. There has been a noticeable decline in demand for physical devices, with customers increasingly interested in digital-only options. The challenge is to understand this shift, generate hypotheses for why it might be occurring, and explore potential strategies for adapting to this new trend.

---

### *Processed Output with System 1 and System 2 Thinking:*

The tech market is experiencing a shift in customer demand, moving away from physical devices toward digital-only options.

[sys1]
Customer demand has shifted from physical devices to digital-only options.
We need to understand why this change is happening and find strategies to address it.
Key factors may include cost, convenience, and technological trends.
[end sys1]

[sys2]
**2.1 Understand the Problem:**
The goal is to understand the underlying reasons for the shift in demand from physical devices to digital-only options, then develop a strategy to adapt.

*Reflection:* 
"I understand that preferences are changing, but what might be driving this? Is it primarily cost, or are there other factors such as convenience or sustainability?"

*Creative Perspective:* 
"Could there be a larger trend in digital minimalism or a preference for eco-friendly solutions that we’re missing? What unseen motivations might explain this shift?"

**2.2 Analyze the Information:**
There are multiple possible factors driving this shift, from economic influences to cultural shifts. It’s essential to isolate each factor and understand its impact.

*Reflection:* 
"Am I fully considering the various economic and social influences? Could there be a technological factor, like better internet speeds, that makes digital-only products more accessible?"

*Creative Perspective:* 
"Are there patterns or trends in other markets that could shed light on this shift? Could this be part of a larger trend toward virtual experiences?"

**2.3 Generate Hypotheses:**
1. Customers prefer digital options due to lower costs. (Confidence: 0.8, Creative: 0.4)
2. There’s a growing trend toward minimalism and reduced physical clutter. (Confidence: 0.7, Creative: 0.7)
3. Digital products offer greater flexibility and ease of use. (Confidence: 0.6, Creative: 0.6)
4. Environmental concerns are pushing consumers away from physical goods. (Confidence: 0.6, Creative: 0.8)
5. Advances in tech make digital-only options more functional. (Confidence: 0.8, Creative: 0.5)
6. Pandemic-era remote work increased demand for digital solutions. (Confidence: 0.7, Creative: 0.6)
7. Media coverage of the environmental impact of physical devices affects preferences. (Confidence: 0.5, Creative: 0.7)
8. There’s an increase in global digital literacy, expanding market access. (Confidence: 0.6, Creative: 0.6)
9. Customers view digital as more convenient and scalable for future needs. (Confidence: 0.7, Creative: 0.5)
10. Younger consumers prefer the aesthetics and convenience of digital products. (Confidence: 0.6, Creative: 0.6)

*Reflection:* 
"Have I considered all possible influences? Are there any surprising factors that could explain this shift?"

*Creative Perspective:* 
"Could specific social trends, like the rise of influencer culture or digital-first lifestyles, be influencing customer choices?"

**2.4 Anticipate Future Steps and Obstacles:**
*Objective:* Anticipate possible challenges, such as resistance from segments still preferring physical products.

*Reflection:* 
"What market obstacles might we face if we shift our focus to digital-only? Are there sub-segments that still prioritize physical products?"

*Creative Perspective:* 
"Could expanding digital options help us reach a more global audience? Are there emerging trends that we could leverage in our strategy?"

[end sys2]

[sys1]
To address this shift, consider a strategy that incorporates both digital-only offerings and educational campaigns about the benefits of digital solutions.
Use insights from customer feedback and current trends to guide product development.
Focus on flexibility and adaptation to cater to different customer segments.
[end sys1]


1. Introduction
===============

Room temperature ionic liquids (RTILs) have been receiving considerable attention as innovative solvents for metal catalyzed organic reactions \[[@b1-ijms-12-03989]--[@b6-ijms-12-03989]\]. Most ionic liquids are based on ammonium, imidazolium, phosphonium, pyridinium, sulphonium, picolinium, pyrrolidinium, thiazolium, oxazolium, and pyrazolium cations. The important properties of ionic liquids, such as affinity to water and miscibility with other solvents, can be adjusted by the proper choice of alkyl substituents and counter anion. The most commonly used ionic liquids in olefin metathesis are 1,3-dialkylimidazolium and 1,2,3-trialkylimidazolium salts. Buijsman and co-workers \[[@b3-ijms-12-03989]\] were the first group that reported the application of ionic liquids as a medium for olefin metathesis. They studied ring closing metathesis (RCM) of several substrates using Grubbs first and second generation catalysts in RTILs, and \[bmim\]\[PF~6~\] was found to be the optimal solvent for the reactions. The activity and recyclability of Grubbs second generation catalyst in the self-cross-metathesis of some terminal olefins in RTILs has also been reported by Tang and co-workers \[[@b7-ijms-12-03989]\]. Self-metathesis of 1-octene in 1,3-dialkylimidazolium and 1,2,3-trialkylimidazolium type ionic liquids have been reported by Williams and co-workers \[[@b8-ijms-12-03989]\]. The results from the study showed that ionic liquids with shorter alkyl chain length enhanced the catalytic activity while the longer ones inhibited it. To overcome the problem associated with the leaching of products into the substrate, many charged catalyst systems have been employed \[[@b9-ijms-12-03989]--[@b14-ijms-12-03989]\].

The present work is an extension of our previous one which highlighted the self-metathesis reaction of methyl oleate in \[bmim\]\[*X*\] type ionic liquids \[[@b15-ijms-12-03989]\]. In this study, we report the self-metathesis of methyl oleate and methyl ricinoleate using the catalysts \[**1**--**4**\] in \[bmim\]\[*X*\] and \[bdmim\]\[*X*\] type ionic liquids ([Scheme 1](#f5-ijms-12-03989){ref-type="fig"}). The study also compares the metathesis activity in \[bdmim\] and \[bmim\] type ionic liquids. Catalyst recycling was also carried out in ionic liquids with the catalysts **1**--**4**.

2. Results and Discussion
=========================

2.1. Self-Metathesis of Methyl Oleate
-------------------------------------

The self-metathesis of methyl oleate was carried out in the presence of ruthenium alkylidene catalysts **1**--**4** at 40 °C. The Hoveyda-Grubbs catalysts **3** and **4** were evaluated in 1-butyl 3-methylimidazolium (bmim) and 1-butyl 2,3-dimethylimidazolium (bdmim) based ionic liquids with different anions (PF~6~^−^, BF~4~^−^ and NTf~2~^−^) ([Scheme 1](#f5-ijms-12-03989){ref-type="fig"}). [Figure 1](#f1-ijms-12-03989){ref-type="fig"} shows the activity of **3** in \[bmim\] and \[bdmim\] type ionic liquids. For catalyst **3**, similar conversions were observed in \[bmim\] and \[bdmim\] type ionic liquids (ILs). As there was not much difference in the catalytic activity, the benefit of selecting a particular IL (among PF~6~^−^, BF~4~^−^ and NTf~2~^−^) was found to be of less importance. For catalyst **4**, the highest activity was found in \[bdmim\]\[BF~4~\] with a conversion of 85% ([Figure 2](#f2-ijms-12-03989){ref-type="fig"}). Comparing the cations of the ionic liquids, the C2-methylated imidazolium cation \[bdmim\] led to a slightly better conversion. The benefit of using \[bdmim\] cation in the ethenolysis of methyl oleate has been previously reported by Thurier *et al.* \[[@b16-ijms-12-03989]\].

To study the effect of temperature on metathesis activity, the reactions were conducted at temperatures 40 °C and 60 °C. The results are summarized in [Table 1](#t1-ijms-12-03989){ref-type="table"}. An increase in substrate conversion was observed with increase in temperature. At both the temperatures, the highest substrate conversion was seen with catalyst **4**. Generally for all the runs, Hoveyda-Grubbs catalyst **4** exhibited good activity, although isomerization and formation of secondary metathesis products \[[@b17-ijms-12-03989]\] seems to be a drawback. Hoveyda-Grubbs catalyst **3** and **4** showed good solubility in ionic liquid compared to Grubbs catalyst **1** and **2**. The reason for the high activity of the Hoveyda-Grubbs second generation catalyst can be attributed to the absence of phosphine ligand. It has been proved that phosphine ligand suppresses the catalyst activity in Ru-catalyzed olefin metathesis \[[@b18-ijms-12-03989]\]. The presence of free phosphine in solution can inhibit coordination of olefins to the transition metal centre by re-association with the active Ru complex. With the non-phosphine Ru complex (catalyst **4**), activation occurs through the loss of O→Ru chelation. The styrenyl ether ligand completes less effectively with olefin substrates for Ru chelation \[[@b19-ijms-12-03989]\]. \[bdmim\] type ILs can prevent the carbene formation of catalyst, which is believed to be formed by the deprotonation of imidazolium cation or from the oxidative addition of imidazolium to Ru centre \[[@b20-ijms-12-03989]\].

2.2. Self-Metathesis of Methyl Ricinoleate
------------------------------------------

The self-metathesis of methyl ricinoleate was carried out in the presence of catalysts **1** and **2** in \[bmim\]\[X\] type ILs. [Table 2](#t2-ijms-12-03989){ref-type="table"} summarizes the activity of catalysts **1**--**4** for the self-metathesis of methyl ricinoleate. For catalyst **1**, the highest activity was shown in **5a** with a substrate conversion of 45% and the activity was found to be in the order PF~6~ \> BF~4~ \> NTf~2~ ([Figure 3](#f3-ijms-12-03989){ref-type="fig"}). For catalyst **2**, the same trend was followed, with the reaction in **5a** yielding the highest conversion of 58% ([Figure 4](#f4-ijms-12-03989){ref-type="fig"}). The primary metathesis products (PMP) obtained from the metathesis of methyl ricinoleate (**A**) were 9-octadecene- 7,12-diol (**B**) and dimethyl 9-octadecenedioate (**C**), as illustrated in [Scheme 2](#f6-ijms-12-03989){ref-type="fig"} \[[@b21-ijms-12-03989]\].

2.3. Catalyst Recycling in Ionic Liquids
----------------------------------------

As solvents, ionic liquids are more advantageous than conventional organic solvents, which make them recyclable and environmentally friendly. It has been reported that the ionic liquids could be reused for at least three runs \[[@b3-ijms-12-03989],[@b16-ijms-12-03989],[@b22-ijms-12-03989],[@b23-ijms-12-03989]\]. In a typical experiment, metathesis reaction was carried out in ionic liquids, and, after extraction of reaction products with heptane (2 × 3 mL), the glass reactor was loaded with fresh methyl oleate and was introduced for a new run.

To study the recyclability, Ru catalysts **1**--**4**, in different ionic liquids, were subjected to consecutive runs ([Table 3](#t3-ijms-12-03989){ref-type="table"}). Grubbs catalyst **1** proved to be stable in three consecutive runs, with the third run resulting in a decreased conversion. Grubbs catalyst **2** showed an increased conversion in the third cycle when compared with catalyst **1**. Comparing the Hoveyda-Grubbs catalysts **3** and **4**, the best result was obtained with catalyst **3**. The results prove that catalyst **3** can be reused for three runs without loss of activity. In spite of good activity in the first run, the second generation Hoveyda-Grubbs catalyst **4** showed low catalytic activity during the second run.

3. Experimental Section
=======================

3.1. Materials and Apparatus
----------------------------

1-Butyl-3-methylimidazolium hexafluorophosphate (\[bmim\]\[PF~6~\]), 1-butyl-3-methylimidazolium tetrafluoroborate (\[bmim\]\[BF~4~\]), 1-butyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide (\[bmim\]\[NTf~2~\]), 1-butyl-2,3-dimethylimidazolium hexafluorophosphate (\[bdmim\]\[PF~6~\]), 1-butyl-2,3- dimethylimidazolium tetrafluoroborate (\[bdmim\]\[BF~4~\]), were all reagent grade chemicals from Sigma-Aldrich. Methyl oleate (≥99%) and methyl ricinoleate (\>99%) were obtained from Sigma-Aldrich and were treated with activated alumina and stored under N~2~ atmosphere at a subzero temperature. Ethyl vinyl ether was purchased from Fluka. Nonadecane purchased from Fluka was used as the internal standard (**IS**). Ruthenium catalysts **1**--**4** were stored under N~2~ and used as purchased from Sigma-Aldrich. Chromatograms were obtained using Varian Star 3400 *CX* GC equipped with a DB-624 capillary column (J&W Scientific, 30 m × 0.53 mm) and a flame ionization detector (FID). The oven temperature was held at 200 °C and then increased to 270 °C at a rate of 20 °C min^−1^. The injector temperature was set at 270 °C and the detector temperature at 300 °C with N~2~ as carrier gas.

3.2. Metathesis Experiments
---------------------------

All the reactions were performed under a N~2~ atmosphere in a glass reactor fitted with a thermometer and a rubber septum. For the reaction in RTILs, 0.5 mL of the substrate was added to 1 mL of ionic liquid and stirred for 10 min to attain the reaction temperature. An internal standard (0.05 g) was added followed by the addition of 12.4 mg of catalyst. All the catalysts were soluble in ILs with the substrate forming a biphasic mixture with ILs. Samples were withdrawn by a syringe at regular time intervals for up to 4 hours. The reaction was terminated by immediately quenching with a few drops of ethyl vinyl ether \[[@b22-ijms-12-03989]\]. The quenched sample was diluted with solvent and analyzed by GC.

4. Conclusions
==============

For the self-metathesis of methyl oleate, Hoveyda-Grubbs catalyst **4** provided the best result with enhanced activity. Similar conversions were observed in all the three \[bmim\]\[*X*\] type ionic liquids selected. However, when compared with \[bdmim\]\[*X*\] type ionic liquids, higher activity was observed, which shows the superiority of \[bdmim\]\[*X*\] type ionic liquids as reaction media. Furthermore, it was found that Hoveyda-Grubbs catalyst **3** could be reused for three consecutive runs without loss of activity. Overall, the use of ionic liquids in the metathesis reaction opens a route for the use of vegetable oil as a renewable source of raw materials for the chemical industry.

![Activity of **3** for the self-metathesis of methyl oleate in different ILs.](ijms-12-03989f1){#f1-ijms-12-03989}

![Activity of **4** for the self-metathesis of methyl oleate in different ILs.](ijms-12-03989f2){#f2-ijms-12-03989}

![Activity of 1 for the self-metathesis of methyl ricinoleate in different ionic liquids.](ijms-12-03989f3){#f3-ijms-12-03989}

![Activity of 2 for the self-metathesis of methyl ricinoleate in different ionic liquids.](ijms-12-03989f4){#f4-ijms-12-03989}

![Ruthenium catalysts and imidazolium ionic salts.](ijms-12-03989f5){#f5-ijms-12-03989}

![Primary metathesis products from self-metathesis of methyl ricinoleate.](ijms-12-03989f6){#f6-ijms-12-03989}

###### 

Activity of **3** and **4** for the self-metathesis of methyl oleate in \[bmim\] and \[bdmim\]\[*X*\] type ionic liquids.

  RTIL   Catalyst   Temperature (°C)   Conversion (%)   Selectivity [a](#tfn2-ijms-12-03989){ref-type="table-fn"} (%)
  ------ ---------- ------------------ ---------------- ---------------------------------------------------------------
  5a     1          40                 57               99
         2                             65               97
         3                             55               99
         4                             78               96
         1          60                 59               99
         2                             75               94
         3                             57               98
         4                             87               93
  5b     1          40                 58               99
         2                             67               96
         3                             56               99
         4                             79               96
         1          60                 61               99
         2                             78               94
         3                             59               97
         4                             87               95
  5c     1          40                 57               99
         2                             64               96
         3                             54               99
         4                             74               97
         1          60                 60               99
         2                             73               96
         3                             59               99
         4                             85               95
  6a     3          40                 57               99
         4                             81               98
         3          60                 60               97
         4                             90               95
  6b     3          40                 58               99
         4                             85               99
         3          60                 60               97
         4          40                 92               95

0.5 mL of MO (MO/Ru ratio = 100), 1 mL of IL, reaction time = 4 h;

selectivity towards PMPs.

###### 

Activity of **1** and **2** for the self-metathesis of methyl ricinoleate.

  RTIL     Catalyst   Temperature (°C)   Conversion (%)   Selectivity [a](#tfn4-ijms-12-03989){ref-type="table-fn"} (%)
  -------- ---------- ------------------ ---------------- ---------------------------------------------------------------
  **5a**   **1**      60                 45               99
           **2**                         58               99
  **5b**   **1**      60                 41               99
           **2**                         56               99
  **5c**   **1**      60                 38               99
           **2**      60                 55               99

0.2 mL of MR (MR/Ru ratio = 100), 0.5 mL of IL, reaction time = 4 h;

selectivity towards PMPs.

###### 

Recycling of catalysts in \[bmim\]\[BF~4~\] [a](#tfn5-ijms-12-03989){ref-type="table-fn"} and \[bdmim\]\[BF~4~\] [a](#tfn5-ijms-12-03989){ref-type="table-fn"},[b](#tfn6-ijms-12-03989){ref-type="table-fn"}.

  Catalyst   Conversion (%)     Selectivity (%)
  ---------- ------------------ -----------------
  **1**      1st run: 57 (58)   99
             2nd run: 56 (56)   99
             3rd run: 42 (45)   98
  **2**      1st run: 67 (72)   99
             2nd run:50 (60)    97
             3rd run:45 (57)    97
  **3**      1st run: 56 (58)   99
             2nd run: 56 (58)   99
             3rd run: 49 (53)   99
             4th run: 22 (30)   99
  **4**      1st run: 74 (85)   99
             2nd run: 40 (54)   95
             3rd run: 15 (23)   95

All reactions were performed at 40 °C for 4 hours, substrate/Ru = 100;

values in bracket are for \[bdmim\]\[BF~4~\].